Method of colouring keratin-containing fibres using diazonium salts

ABSTRACT

The present invention relates to a method of colouring keratin-containing fibres, especially human hair, in which method a compound of formula (I), wherein R is hydroxy or NHR 1 , R 1  being hydrogen or C 1 -C 4 alkyl, and B is an aromatic or heterocyclic ring, is diazotised, and the resulting diazonium salt is applied at a pH of from 2 to 5 to the material being coloured and then, by means of increasing the pH to from 7 to 12, is fixed on the material in the form of an oligomeric or polymeric colorant.

[0001] The present invention relates to a method of colouringkeratin-containing fibres, especially human hair, using developer dyes,that is to say dyes which are formed inside the pores of the substrate.

[0002] Colouring with the aid of developer dyes has been known for along time and has also been generally used for dyeing cotton. The dyesand the colouring methods used therefor do not, however, providesatisfactory results for colouring hair.

[0003] For colouring hair, therefore, oxidation dyes are used in mostcases; however, they too are not capable of satisfying all requirements.The fastness to washing properties are often inadequate and, inaddition, the colouring conditions required often cause a greater orlesser amount of damage to the hair.

[0004] DE-A-30 09 833, furthermore, discloses a method of colouring hairwherein a priming cream comprising a specific coupling component and adiazonium salt in the acid range is applied to the hair and the azocoupling reaction is then brought about by means of reaction with analkaline shampoo.

[0005] There is, at present, still a need for a colouring method whichdoes not have the disadvantages of previous colouring methods, forexample the limited stability of the colouring solutions or creams orthe inadequate substantivity and penetration of the colouringcompositions, or which has them to an insignificant degree.

[0006] The present invention relates to a method of colouringkeratin-containing fibres, especially human hair, in which method acompound of formula

[0007] wherein

[0008] R is hydroxy or NHR₁, R₁ being hydrogen or C₁-C₄alkyl, and B isan aromatic or heterocyclic ring, is diazotised, and the resultingdiazonium salt is applied at a pH of from 2 to 5 to the material beingcoloured and then, by means of increasing the pH to from 7 to 12, isfixed on the material in the form of an oligomeric or polymericcolorant.

[0009] The colorations obtained are distinguished by outstandingfastness to washing properties, which are significantly better than inthe case of colorations with oxidation dyes, and there is virtually nodamage to the hair. Moreover, there is no staining of the scalp, becausethe dye components do not penetrate into the skin and non-fixed dye canbe washed off readily.

[0010] The method of the invention is distinguished by the fact that asystem consisting of a coupling component and a separate diazonium saltis not used, but rather only a diazonium salt of the compound of formula(1), a so-called “precursor”, is used, which functions both as couplingcomponent and as diazo component.

[0011] Preparation of the “precursors” by diazotisation of the compoundsof formula (1) is carried out using generally known methods, in a mannerknown per se, for example with sodium nitrite in an acidic, for examplehydrochloric-acid-containing or sulfuric-acid-containing, aqueousmedium. The diazotisation may, however, also be carried out using otherdiazotisation agents, e.g. with nitrosylsulfuric acid. In thediazotisation, an additional acid may be present in the reaction medium,e.g. phosphoric acid, sulfuric acid, acetic acid, propionic acid,hydrochloric acid or mixtures of such acids, e.g. mixtures of propionicacid and acetic acid. The diazotisation is advantageously carried out attemperatures of from −10 to 30° C., for example from −10° C. to roomtemperature.

[0012] The diazotised compounds of formula (1) correspond to formula

[0013] wherein R and B are as defined for formula (1) and A⁻ is ananion.

[0014] Suitable anions A⁻ are both inorganic and organic anions, forexample halide, such as chloride, bromide or iodide, sulfate, hydrogensulfate, methyl sulfate, formate, acetate and lactate.

[0015] The anion is generally determined by the preparation process.Preferably, the chlorides, hydrogen sulfates, sulfates, methosulfates oracetates are present.

[0016] Among the compounds of formula (1), the compounds of formulae

[0017] wherein

[0018] R₂ is hydroxy or NHR₁, R₁ being hydrogen or C₁-C₄alkyl,

[0019] R₃ is C₁-C₄alkyl or sulfo,

[0020] R₄ is hydroxy or sulfo,

[0021] R₅ is hydrogen, C₁-C₄alkyl, —COOH or COOC₁-C₄alkyl,

[0022] R₆ and R₇ are, each independently of the other, hydrogen orC₁-C₄alkoxy,

[0023] n is a number 0, 1 or 2, and

[0024] m is a number 0, 1 or 2,

[0025] are especially important for the preparation of the “precursors”.

[0026] The compounds of formulae (1) to (6) are known, for example, fromU.S. Pat. No. 1,892,480 and CH-A-154 172 or can be prepared in a mannerknown per se.

[0027] Preferred “precursors” are the compounds of formulae

[0028] wherein A₁ ⁻ is a chloride, sulfate, hydrogen sulfate, zincchloride, fluoroborate, oxalate or 1,5-naphthalenedisulfonate anion oranother aromatic sulfonate anion.

[0029] The colouring method according to the invention comprisesapplying to the material being coloured a diazonium salt of a compoundof formula (1) under conditions such that, initially, a couplingreaction does not take place, which is achieved preferably bymaintaining a pH of from 2 to 5, preferably from 3 to 4.

[0030] For carrying out the colouring method, the diazonium salt of thecompound of formula (1) is applied in a solution, cream, emulsion or gelto the material being coloured. Lowering the pH is achieved inconventional manner by adding an acid or, preferably, a suitable buffersolution.

[0031] After a contact time of from 1 to 20 minutes, preferably from 2to 10 minutes, the coupling reaction is brought about by increasing thepH to a value of from 7 to 12, especially from 7.5 to 10, moreespecially from 8 to 9, advantageously by applying an alkaline shampoo.

[0032] Any customary shampoo formulation based on anionic, or preferablynon-ionic, surfactants, which has been adjusted to a pH of from 7 to 12by the addition of, for example, sodium carbonate, can be used as theshampoo for increasing the pH and initiating the azo coupling.

[0033] The coloured material is then finished in customary manner, forexample by rinsing with water and then drying.

[0034] The method according to the invention is used for colouringkeratin-containing fibres and especially for colouring hair. The hairmay be the hair of wigs or, especially, the living hair of animals and,more especially, humans.

[0035] The invention relates also to a colouring composition forcarrying out the method according to the invention, which compositioncomprises

[0036] a) at least a compound of formula (1a),

[0037] b) a medium for adjusting the pH,

[0038] c) water

[0039] and, optionally,

[0040] d) further additives.

[0041] A preferred colouring composition for carrying out the methodaccording to the invention comprises, as component a), the compound offormula (7), (8), (9), (10) or (11).

[0042] The multiplicity of shades of the dye, which results by themethod according to the present invention, can be increased bycombination with other dyes.

[0043] The present invention relates also to the colouration of hairwith a dye, which results by the method according to the presentinvention, and at least one other dye.

[0044] The dye, which results by the combination of at least one cappeddiazonium compound and at least one coupling compound, can be combinedwith dyes of the same or different class of dyes, especially with directdyes, oxidation dyes; dye precursor combinations of a coupler compoundand a diazotized compound, or a capped diazotized compound; and/orcationic reactive dyes.

[0045] Direct dyes are natural or synthetic, they are uncharged,cationic or anionic, such as acid dyes.

[0046] Oxidation dye denotes also for oxidation dye precursors, whichare from the group of the developer and coupler compounds.

[0047] In the context of the invention the single classes of dyescomprise the dyes defined in the Color Index of the Society of TextileChemist and Colorist.

[0048] Preferably the compositions, formulations, methods and processescomprise at least a single compound of formula (1) or (1a).

[0049] In the following suitable direct dyes for the combination withthe method according to the present invention are described.

[0050] Directs dyes are for example described in “Dermatology”, editedby Ch. Culnan, H. Maibach, Verlag Marcel Dekker Inc., New York, Basle,1986, Vol. 7, Ch. Zviak, The Science of Hair Care, chapter 7, pages248-250, and

[0051] in “Europäisches Inventar der Kosmetikrohstoffe”, 1996, publishedby The European Commission, obtainable in diskette form from theBundesverband der deutschen Industrie-und Handelsunternehmen fürArzneimittel, Reformwaren und Körperpflegemittel e.V., Mannheim.

[0052] Preferred direct dyes, which are suitable as single dye or incombination with other direct dyes, especially for semi permanentdyeing, are:

[0053] 2-Amino-3-nitrophenol, 2-Amino-4-hydroxyethylamino-anisolesulfate, 2-Amino-6-chloro-4-nitrophenol,2-Chloro-5-nitro-N-hydroxyethylene-p-phenylendiamine,2-Hydroxyethyl-picramic acid,2,6-Diamino-3-((pyridine-3yl)-azo)pyridine,2-Nitro-5-glyceryl-methylaniline, 3-Methylamino-4-nitro-phenoxyethanol,4-Amino-2-nitrodiphenyleneamine-2′-carboxilic acid,6-Nitro-1,2,3,4,-tetrahydroquinoxaline,4-N-Ethyl-1,4-bis(2′-hydroxyethylamino-2-nitrobenzene hydrochloride,1-Methyl-3-nitro-4-(2′-hydroxyethyl)-aminobenzene,3-Nitro-p-hydroxyethyl-aminophenol, 4-Amino-3-nitrophenol,4-Hydroxypropylamine-3-nitrophenol (BN),Hydroxy-anthrylaminopropylmethyl morphlino methosulfat,4-Nitrophenyl-aminoethylurea, 6-Nitro-p-toluidine, Acid Blue 62, AcidBlue 9, Acid Red 35, Acid Red 87 (Eosin), Acid Violet 43, Acid Yellow 1,Basic Blue 3, Basic Blue 6, Basic Blue 7, Basic Blue 9, Basic Blue 12,Basic Blue 26, Basic Blue 99, Basic Brown 16, Basic Brown 17, Basic Red2, Basic Red 22, Basic Red 76, Basic Violet 14, Basic Yellow 57, BasicYellow 9, Disperse Blue 3, Disperse Orange 3, Disperse Red 17, DisperseViolet 1, Disperse Violet 4, Disperse Black 9, Fast Green FCF, HC-Blue2, HC-Blue 7, HC-Blue 8, HC-Blue 12, HC-Orange 1, HC-Orange 2, HC-Red 1,HC-Red 10-11, HC-Red 13, HC-Red 16, HC-Red 3, HC-Red BN, HC-Red 7,HC-Violet 1, HC-Violet 2, HC-Yellow 2, HC-Yellow 5, HC-Yellow 5,HC-Yellow 6, HC-Yellow 7, HC-Yellow 9, HC-Yellow 12, HC-Red 8,Hydroxyethyl-2-nitro-p-toluidine,N,N-Bis-(2-Hydroxyethyl)-2-nitro-p-phenylendiamine (BS), Picramic Acid,Solvent Green 7.

[0054] Also, cationic azo dyes, for example according to GB-A-2 319 776as well as the oxazine dyes described in DE-A-299 12 327 and mixturesthereof with the other direct dyes mentioned therein, are likewisesuitable for combination.

[0055] Preferred direct dyes, which are suitable as single dye or incombination with other direct dyes or oxidative dyes and oxidizationagents, especially for semi permanent dyeing and permanent dyeing, are:

[0056] Disperse Violet 4, Picramic acid,N,N′-Bis-(2-Hydroxyethyl)-2-nitro-p-phenylendiamine, HC Yellow No. 5, HCBlue No. 2, HC Yellow No.2,2-Chloro-5-nitro-N-hydroxyethyl-p-phenylendiamine, HC Red No.3,4-Amino-3-nitrophenol, Basic Blue 99, 2-Hydroxyethyl Picramic acid, HCYellow No. 6, Hydroxyethyl-2-nitro-p-toluidine,2-Amino-6-chloro-4-nitrophenol, 4-Hydroxypropylamino-3-nitrophenol,Basic Red 2, HC Red No. 16 and HC Blue No. 16.

[0057] In the following suitable cationic dyes for the combination withthe method according to the present invention are described.

[0058] Preferred cationic dyes are described

[0059] in WO 95/01772, especially on page 2, line 7 to page 4, line 1,and especially on page 4, line 35 to page 8, line 21 and on pages 11 to27, or

[0060] in WO 01/66646, especially on page 1, line 18 to page 3, line 16,and preferred from page 16, line 20 to page 22, and cationic dyes asdescribed on pages 10 to 17, or

[0061] in EP 970 685, especially on page 2, line 44 to page 9, line 56and preferably on page 9, line 58 to page 48, line 12, or

[0062] direct dyes are described in DE-A-19 713 698, especially page 2,line 61 to page 3, line 43, or

[0063] direct dyes and oxidizing agent are described in WO 97/20545,especially on page 1, lines 4 to 10, in particular on page 3, lines 24to 32, and on page 11, line 6 to page 13, line 19, especially withdirect dyes are described on page 5, line 28 to page 8, line 20, or

[0064] cationic dyes and anionic UV-absorbers are described in EP 1 166752, especially on page 3, line 20 to page 4, line 21, in particularwith UV absorber on page 4, lines 26 to 3, and especially on page 7,line 47 to page 9, line 56.

[0065] More preferred are cationic dyes such as Basic Yellow 87, BasicOrange 31 or Basic Red 51, or cationic dyes as described in WO 01/66646,especially cationic dye of example 4, or cationic dyes as described inWO 02/31056, especially cationic dye of example 6, compound of formula106.

[0066] Also very suitable for combination with the method according tothe invention are cationic nitroaniline and anthraquinone dyes, forexample those described in the following patent specifications: U.S.Pat. No. 5,298,029, especially in column 2, line 33 to column 5, line38; U.S. Pat. No. 5,360,930, especially in column 2, line 38 to column5, line 49; U.S. Pat. No. 5,169,403, especially in column 2, line 30 tocolumn 5, line 38; U.S. Pat. No. 5,256,823, especially in column 4, line23 to column 5, line 15; U.S. Pat. No. 5,135,543, especially in column4, line 24 to column 5, line 16; EP-A-818 193, especially on page 2,line 40 to page 3, line 26; U.S. Pat. No. 5,486,629, especially incolumn 2, line 34 to column 5, line 29; and EP-A-758 547, especially onpage 7, line 48 to page 8, line 19.

[0067] Also very suitable for combination with the method according tothe invention are mixtures of cationic dyes with other dyes:

[0068] mixtures of at least two cationic dyes as described in WO95/01772, especially on page 8, line 34 to page 10, line 22 with thegiven preferences, or

[0069] combinations of Pyrazolo-[1,5-a]-pyrimidines with at least onecationic dye as described in EP 998,908, especially on page 2, line 34to line 42, with preferred Pyrazolo-[1,5-a]-pyrimidines as described inEP 998,908, especially on page 2, line 48 to page 4, line 3, and withpreferred cationic direct dyes as described in EP 998,908, especially onpage 4, line 22 to page 47, line 24, or

[0070] combinations of cationic dyes as described in FR-2788432,especially on page 53, line 1 to page 63, line 23, especially acombination of cationic dyes with Arianors in FR-2788432, especially onpages 51 to 52, or especially a combination with at least one BasicBrown 17, Basic brown 16, Basic Red 76 and Basic Red 118, and/or atleast one Basic Yellow 57, and/or at least one Basic Blue 99, or

[0071] combinations of direct dyes and/or an oxidation dye and oxidizingagents in the form of permanent-wave fixing solution, especially withdirect dyes as described in DE-A-19 713 698, especially page 4, line 65to page 35, line 59, or

[0072] combinations of cabonic dyes and an oxidation dye of thedeveloper compound type and oxidizing agents as described in EP 850 638,especially on page 2, line 27 to page 7, line 46 and preferred on page7, line 20 to page 9, line 26; or

[0073] combinations of an extemporaneous mixture of a composition (A)containing one or more oxidation dye precursors and optionally one ormore couplers, and of a composition (B), in powder form, containing oneor more direct dye, preferably cationic, optionally dispersed in anorganic pulverulent excipient and/or a mineral pulverulent excipient,and a composition (C) containing one or more oxidizing agent asdescribed in U.S. Pat. No. 6,190,421, especially in column 2, lines 2 to1, and preferably with oxidation dye precursors as described in column2, line 35 to column 5, line 13, and preferably with direct dyes asdescribed in column 5, line 30 to column 7, line 14, or

[0074] a ready-to-use composition comprising, at least one oxidationbase, at least one cationic direct dye and at least one enzyme of2-electron oxidoreductase type in the presence of at least one donor forthe said enzyme as described in U.S. Pat. No. 6,228,129, especially incolumn 26, line 26 to column 27, line 9 with cationic direct dyes asdescribed in column 8, line 17 to column 13, line 65, especially thoseas described in column 20, line 11 to line 19, in column 23, line 61 tocolumn 24, line 25, or

[0075] compositions of at least one direct cationic dye and at least onenitrated benzene dye as described in WO 99/20235 on page 2, line 1 topage 7, line 9, and on page 39, line 1 to page 40b line 11, withcationic direct dyes as described on page 8, line 12 to page 25 line 6,and nitro benzene direct dyes as described on page 26, line 7 to page30, line 15, or

[0076] compositions of at least one direct cationic dye and at least oneautooxidisable oxidation dye, especially benzene, indol and indolinederivatives as described in WO 99/20234, with in preferred direct dyesas given on page 2, line 17 to page 26, line 4, and autooxidisableoxidation dye as described especially on page 26, line 10 to page 28,line 15, or

[0077] oxidation dyeing compositions of at least one direct dye and atleast one meta-Aminophenol derivative and at least one developercompound and an oxidizing agent as described in EP 850 636, especiallyon page 5, line 41 to page 7, line 52, and preferably on page 19, line50 to page 22, line 12, with preferred direct dye as described on page18, lines 1 and 2 in connection with page 7, line 53 to page 17, line55, and with preferred meta-Aminophenol derivatives as described on page7, line 47 to line 52, and with preferred developer compounds asdescribed on page 6, line 10 to page 7, line 46, or

[0078] oxidation dyeing compositions of at least one direct dye and atleast one developer compound selected from the group ofpara-Phenylenediamine derivatives and Bis-Phenylalkylenediamine and, andat least one coupler compound selected from the group of meta-Diphenolsand an oxidizing agent, as described in EP-A-850 637, especially on page6, line 50 to page 8, line 44,

[0079] oxidation dyeing compositions with cationic couplers, asdescribed in WO 99/48856, especially on page 9, line 16 to page 13, line8, and page 11, line 20 to page 12, line 13, or

[0080] cationic dye and e.g. a pyrazolo-(1,5-a)-pyrimidine derivatives,as described in EP 998 908, especially on page 2, line 34 to page 4,line 23, or

[0081] arianoren and/or oxidative dyes, as described in FR-2 788 432,especially on page 2, line 16 to page 3, line 16, and page 5, line 19 topage 14, line 8, and combinations with cationic dyes as described onpage 14, line 23 and following, or

[0082] oxidative dye precursors (unsaturated aldehyde and couplercompounds), as described in German Patent Application 197 172 24,especially unsaturated aldehydes as described on page 2, line 50 to line66 and page 3 line 8 to line 12 are used as developer compounds, andprimary and secondary amino group compounds, nitrogen-containingheterocyclic compounds, amino acids, oligopeptids, aromatic hydroxycompounds, CH-active compounds as described on page 3, line 42 to page 5line 25 are used as coupler compounds.

[0083] Also cationic azo dyes, e.g. according to GB-A-2 319 776, as wellas the oxazine dyes described in DE-A-29 912 327 and mixtures thereofwith the other direct dyes mentioned therein, can likewise readily becombined.

[0084] More preferred are cationic dyes such as Basic Yellow 87, BasicOrange 31 or Basic Red 51, or as described in WO 01/66646, especiallycationic dye of example 4, or as described in WO 02/31056, especiallycationic dye of example 6, compound of formula 106.

[0085] Especially preferred direct dye mixtures comprising a dye offormula (1) of WO 01/66646, especially a direct dye of example 4, and/oror a dye of formula (2) of WO 02/31056, especially a direct dye ofexample 6, and/or Basic Yellow 87, and/or Basic Red 51, and/or BasicOrange 31.

[0086] No particular limitation is imposed on the acid dye used in thepresent invention so far as it is a water-soluble acid dye.

[0087] For the purpose of further modification of color shades, themethod of colouring according to the invention may comprise customaryacid dyes, for example from the group of the compounds known by theinternational names (Color index), or trade names.

[0088] Preferred examples of acid dyes are described in U.S. Pat. No.6,248,314, they include Red Color No. 120, Yellow Color No. 4, YellowColor No. 5, Red Color No. 201, Red Color No. 227, Orange Color No. 205,Brown Color No. 201, Red Color No. 502, Red Color No. 503, Red Color No.504, Red Color No. 506, Orange Color No. 402, Yellow Color No. 402,Yellow Color No. 406, Yellow Color No. 407, Red Color No. 213, Red ColorNo. 214, Red Color No. 3, Red Color No. 104, Red Color No. 105(1), RedColor No. 106, Green Color No. 2, Green Color No. 3, Orange Color No.207, Yellow Color No. 202(1), Yellow Color No. 202(2), Blue Color No.202, Blue Color No. 203, Blue Color No. 205, Blue Color No. 2, YellowColor No. 203, Blue Color No. 201, Green Color No. 201, Blue Color NO.1, Red Color No. 230(1), Red Color No. 231, Red Color No. 232, GreenColor No. 204, Green Color No. 205, Red Color No. 401, Yellow Color No.403(1), Green Color No. 401, Green Color No. 402, Black Color No. 401and Purple Color No. 401, especially Black Color No. 401, Purple Color401, Orange Color No. 205.

[0089] These acid dyes may be used either single or in any combinationthereof.

[0090] Preferably they are incorporated in a proportion of 0.001-5% byweight (hereinafter indicated merely by “%”), particularly 0.005-4%,more particularly 0.2-3% based on the total weight of the composition,from the viewpoint of practical use in that a sufficient hair-dyeingeffect is achieved, and the hand skin is scarcely smeared.

[0091] Also very suitable for combination with the method according tothe invention are uncharged dyes, for example from the group of thenitroanilines, nitrophenylenediamines, nitroaminophenols,anthraquinones, indophenols, phenazines, phenothiazines, bispyrazolonsor bispyrazol aza derivatives or methines.

[0092] Also very suitable for combination with the method according tothe invention are oxidation dyes.

[0093] Suitable oxidation dyes are described for example in

[0094] German Patent Application 19 94 450, especially on page 6, line 6to line 64, or

[0095] German Patent Application 19 959 479, especially in column 2,line 6 to column 3, line 11, or

[0096] in the series “Dermatology”, edited by Ch. Culnan, H. Maibach,Verlag Marcel Dekker Inc., New York, Basle, 1986, Vol. 7, Ch. Zviak, TheScience of Hair Care, chapter 8, on pages 264-267 (oxidation dyes), or

[0097] in German Patent Application 19 717 224; unsaturated aldehydes asdescribed on page 2, line 50 to line 66 and on page 3 line 8 to line 12are used as developer compounds, and primary and secondary amino groupcompounds, nitrogen-containing heterocyclic compounds, amino acids,oligopeptids, aromatic hydroxy compounds, CH-active compounds asdescribed on page 3, line 42 to page 5 line 8 are used as couplercompounds.

[0098] Oxidation dye precursors of the developer type are for exampleprimary aromatic amines, which are substituted in the para- orortho-position with a substituted or unsubstituted hydroxy- or aminoresidue, or diaminopyridine derivatives, heterocyclic hydrazones,4-amino-pyrazol derivatives, 2,4,5,6-tetraminopyrimidin derivatives, orunsaturated aldehydes as described in German Patent Application 19 717224, especially on page 2, line 50 to line 66 and on page 3 line 8 toline 12, or cationic developer compounds as described in WO 00/43367,especially on page, 2 line 27 to page 8, line 24, in particular on page9, line 22 to page 11, line 6.

[0099] Also very suitable for combination with the method according tothe invention are developer dyes in their physiological compatible acidaddition salt form, such as hydrochloride or sulfate. Developer dyeswhich have aromatic OH substituents are also suitable in their salt formwith base, such as alkalimetalphenolates.

[0100] Preferred developer compounds are:

[0101] 1,4-diamino-benzene (p-phenylendiamine),1,4-diamino-2-methyl-benzene (p-toluylen-diamine),1,4-diamino-2,6-dimethyl-benzene, 1,4-diamino-2,5-dimethyl-benzene,1,4-diamino-2,3-dimethyl-benzene, 2-chloro-1,4-diaminobenzene,4-phenylamino-aniline, 4-di-methylamino-aniline, 4-diethylamino-aniline,hydroxyethyl-p-phenylendiamine, 1-(2′-hydroxy-ethyl)-2,5-diaminobenzene,N,N-bis-(2-hydroxyethyl)-p-phenylendiamine,4-[(2-methoxyethyl)amino]-aniline, 4-[(3-hydroxypropyl)amino]-aniline,hydroxypropyl-bis-(N-hydroxyethyl-p-phenylenediamine) hydrochloride,1,4-diamino-2-(2-hydroxyethyl)-benzene,1,4-diamino-2-(1-methylethyl)-benzene, 2-(2,5-diaminophenoxy)-ethanol,1,3-bis[(4-aminophenyl)(2-hydroxyethyl)amino]-2-propanol,bis-(2-hydroxy-5-aminophenyl)-methane,1,4-bis-(4-aminophenyl)-diazacycloheptane,1,8-bis(2,5-diaminophenoxy)-3,6-dioxaoctan,1,10-bis-(2,5-diaminophenyl)-1,4,7,10-tetraoxadecane,hydroxyethyl-3,4-methylenedioxyaniline, p-aminophenol, o-aminophenol,m-aminophenol, 2-amino-6-methyl-phenol, 4-methylaminophenol sulfate,4-amino-m-cresol, 6-amino-m-cresol, 6-amino-m-cresol,2-amino-4-hydroxyethylaminoanisole, 2-amino-5-methyl-phenol,4-amino-3-methylphenol, 4-methylamino-phenol,2-aminomethyl-4-aminophenol,4-amino-2-[(2-hydroxyethyl)-amino]methyl-phenol,4-amino-2-(2-hydroxyethoxy)-phenol, 4-amino-2-(methoxymethyl)-phenol,4-amino-2-(2-hydroxyethyl)-phenol, 2-hydroxymethylamino-4-aminophenol,bis-(4-aminophenyl)amine, 4-amino-3-fluorphenol,2-hydroxymethyl-4-aminophenol, 4-amino-2-(diethylamino)-methyl)-phenol,5-amino-salicylsaure, 2,5-diamino-pyridine, 2-amino-3-hydroxy-pyridine,2,6-dimethoxy-3,5-diamino-pyridine, 2,4,5,6-tetraminopyrimidine,2-hydroxy-4,5,6-triaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine,2,4-dihydroxy-5,6-diaminopyrimidine,2-dimethylamino-4,5,6-triaminopyrimidine,2,5,6-triamino-4-(1H)-pyrimi-done, further 4,5-diaminopyrazolderivatives as described in EP 0 740 741 or WO 94/08970, especially4,5-diamino-1-(2-hydroxyethyl)-1H-pyrazol,4,5-diamino-1-(1-methylethyl)-1H-pyrazol,4,5-diamino-1-[(4-methylphenyl)methyl]-1H-pyrazol,1-[(4-chlorophenyl)methyl]-4,5-diamino-1H-pyrazol,4,5-diamino-1-methyl-1H-pyrazol.

[0102] More preferred developer dyes are p-phenylendiamine,p-toluylendiamine, p-aminophenol, m-aminophenol, o-aminophenol,N,N-bis-(2-hydroxyethyl)-p-phenylendiamine sulfate,2-amino-4-hydroxyethylaminoanisole sulfate,hydroxyethyl-3,4-methylenedioxyaniline,1-(2′-hydroxyethyl)-2,5-diaminobenzene,2,6-dimethoxy-3,5-diamino-pyridine,hydroxypropyl-bis-(N-hydroxyethyl-p-phenylenediamine) hydrochloride,hydroxyethyl-p-phenylendiamine sulfate, 4-amino-3-methylphenol,4-methylaminophenol sulfate, 2-aminomethyl-4-aminophenol,4,5-diamino-1-(2-hydroxyethyl)-1H-pyrazol, 4-amino-m-cresol,6-amino-m-cresol, 5-amino-6-chloro-cresol, 2,4,5,6-tetraminopyrimidine,2-hydroxy-4,5,6-triaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidinesulfate.

[0103] Preferred oxidation dye precursors of the coupler type are forexample m-phenylendiamine derivatives, naphthole, resorcine andresorcine derivatives, pyrazolone and m-aminophenol derivatives.

[0104] Especially preferred coupler compounds areN-(3-dimethylamino-phenyl)-urea, 4-amino-2-hydroxytoluene,2-methyl-5-hydroxyethylaminophenol, 2,4-diaminophenoxyethanol,2-amino-4-[(2-hydroxyethyl)amino]-anisole, p-aminophenol, m-aminophenoland its derivatives, especially 5-amino-2-methylphenol,5-(3-hydroxypropylamino)-2-methylphenol,3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol,2,6-dimethyl-3-aminophenol,3-trifluoroacetylamino-2-chloro-6-methylphenol,5-amino-4-chloro-2-methylphenol, 5-amino-4-methoxy-2-methylphenol,5-(2′-hydroxyethyl)-amino-2-methylphenol, 3-(diethylamino)-phenol,N-cyclopentyl-3-aminophenol, 1,3-dihydroxy-5-(methylamino)-benzene,3-(ethyl-amino)-4-methylphenol and 2,4-dichloro-3-aminophenol,

[0105] o-aminophenol and its derivatives, such as5-methyl-2-(1-methylamino)-phenol, 3-di-methylamino-phenol,3-diethylamino-phenol, 5-amino-2-methyl-phenol,5-amino-4-fluor-2-methyl-phenol, 5-amino-4-methoxy-2-methyl-phenol,5-amino-4-ethoxy-2-methyl-phenol, 3-amino-2,4-dichlor-phenol,5-amino-2,4-dichlor-phenol, 3-amino-2-methyl-phenol,3-amino-2-chlor-6-methyl-phenol, 3-amino-phenol,2-[(3-hydroxy-phenyl)amino]-acetamide,5-[(2-hydroxyethyl)amino]-2-methyl-phenol,3-[(2-hydroxy-ethyl)amino]-phenol, 3-[(2-methoxyethyl)amino]-phenol,5-amino-2-ethyl-phenol, 2-(4-amino-2-hydroxyphenoxy)-ethanol,5-[(3-hydroxypropyl)amino]-2-methyl-phenol,3-[(2,3-dihydroxypropyl)amino]-2-methyl-phenol,3-[(2-hydroxyethyl)amino]-2-methyl-phenol,

[0106] m-diaminobenzene and its derivatives such as2,4-diaminophenoxyethanol, 1,3-bis-(2,4-diaminophenoxy)-propane,1-methoxy-2-amino-4-(2′-hydroxyethylamino)-benzene,1,3-bis-(2,4-diaminophenyl)-propane, 3-[(2-aminoethyl)amino]-aniline,1,3-di(2,4-diaminophenoxy)-propane, 1,3-diamino-2,4-dimethoxy-benzene,2,6-bis(2-hydroxyethyl)amino-toluene, di(2,4-diaminophenoxy)-methane,3-[di(2-hydroxyethyl)amino]-aniline,2,6-bis-(2-hydroxyethylamino)-1-methylbenzene and1-amino-3-bis-(2′-hydroxyethyl)-aminobenzene,

[0107] o-diaminobenzene and its derivatives such as 3,4-diaminobenzoicacid and 2,3-diamino-1-methylbenzene,2,4-diamino-1-fluor-5-methyl-benzene,2,4-diamino-1-methoxy-5-methyl-benzene,1-(2-aminoethoxy)-2,4-diaminobenzene,2-amino-1-(2-hydroxyethoxy)-4-methylamino-benzene,2,4-diaminophenoxy-acetic acid, 2,4-di-amino-1-ethoxy-5-methyl-benzene,3-[(2-hydroxyethyl)amino]-aniline, 3,4-diamino-benzoic acid,3,4-dihydro-6-hydroxy-1,4(2H)-benzoxazine,6-amino-3,4-dihydro-1,4(2H)-benzoxazine,2,4-diamino-1,5-di(2-hydroxyethoxy)-benzene,2,4-diamino-1-(2-hydroxyethoxy)-5-methyl-benzene,4-amino-2-di[(2-hydroxyethyl)amino]-1-ethoxy-benzene2,4-di[(2-hydroxyethyl)amino]-1,5-dimethoxy-benzene,3,4-dihydro-6-hydroxy-1,4(2H)-benzoxazine,6-amino-3,4-dihydro-1,4(2H)-benzoxazine,

[0108] di- or trihydroxybenzene derivatives such as resorcine,resorcinmonomethylether, 2-methylresorcine, 5-methylresorcine,2,5-dimethylresorcine, 1-chloro-2,4-dihydroxy-benzene,2-chlororesorcine, 4-chlororesorcine, 2,6-dihydroxyethylaminotoluene,1,2-dichlor-3,5-dihydroxy-4-methyl-benzene,1,5-dichlor-2,4-dihydroxy-benzene, 1,3-di-hydroxy-2-methyl-benzene,pyrogallol and 1,2,4-trihydroxybenzene,

[0109] pyridine derivatives such as 2,6-diamino-pyridine,2,6-dihydroxypyridine, 2-amino-3-hydroxypyridine,2-amino-5-chloro-3-hydroxypyridine, 5-amino-4-chloro-2-methyl-phenol,3-diamino-6-methoxy-pyridine, 3-amino-2-methylamino-6-methoxypyridine,2,6-dihydroxy-3,4-dimethylpyridine, 2,6-dihydroxy-4-methylpyridine,2,6-diamino-pyridine, 2,3-diamino-6-methoxypyridine,2,6-diamino-3,5-dimethoxy-pyridine, and3,5-diamino-2,6-dimethoxypyridine,

[0110] naphthaline derivatives such as 1-naphthol, 2-methyl-1-naphthol,2-hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol,1,5-dihydroxynaphthaline, 1,6-dihydroxy-naphthaline,1,7-dihydroxynaphthaline, 1,8-dihydroxynaphthaline,2,7-dihydroxy-naphthaline and 2,3-dihydroxynaphthaline,2-methyl-1-naphthol-acetat,

[0111] morpholine derivatives such as 6-hydroxybenzomorpholine and6-aminobenzo-morpholine,

[0112] chinoxaline derivatives such as6-methyl-1,2,3,4-tetrahydrochinoxaline,

[0113] pyrazol derivatives such as -phenyl-3-methylpyrazol-5-one,3-methyl-1-phenyl-5-pyrazolone,

[0114] indol derivatives such as 4-hydroxyindol, 5-hydroxy-indol,6-hydroxyindol and 7-hydroxyindol, 2,3-indolindione,5,6-dihydroxy-indol, 5,6-dihydroxy-indoline,

[0115] methylendioxybenzene derivates such as1-hydroxy-3,4-methylendioxybenzene, 1-amino-3,4-methylendioxybenzene and1-(2′-hydroxyethyl)-amino-3,4-methylendioxybenzene,3,4-methylendioxy-phenol, 3,4-methylendioxy-aniline,5-[(2-hydroxy-ethyl)amino]-1,3-benzodioxol,6-brom-1-hydroxy-3,4-methylendioxy-benzene, or

[0116] cationic coupler compounds as described in FR 2 794 644,especially on page 11, line 20 to page 15, line 34, and on page 17,lines 4 to 12, page 178, line 33 to page 18, line 24.

[0117] More especially preferred coupler compounds aretoluene-2,5-diamine sulfate, 1-naphthol, 1,5-, 2,7- and1,7-dihydroxynaphthaline, 3-aminophenol, 5-amino-2-methylphenol,2-amino-3-hydroxypyridine, resorcinol, 4-chlororesorcine,2-chloro-6-methyl-3-aminophenol, 2,6-di-hydroxyethylaminotoluene,2-methyl-5-dihydroxyethylaminophenol, 2,4-diaminophenoxy-ethylolhydrochloride, 2-methylresorcine, 5-methylresorcine,2,5-dimethylresorcine, 3,4-methylenedioxyphenol,2-amino-4-hydroxyethylaminoanisole sulfate,2,6-di-(beta-hydroxy-ethylamino)-toluene, 4-amino-2-hydroxytoluene,6-hydroxyindol, 2-amino-3hydroxypyridine,2,6-dimethoxy-3,5-pyridinediamine hydrochloride and2,6-dihydroxy-3,4-dimethylpyridine.

[0118] Most preferred coupler compounds are2-chloro-6-methyl-3-aminophenol, 5-amino-2-methylphenol,2-amino-3-hydroxypyridine, 2,6-di-(beta-hydroxyethylamino)-toluol,2-methylresorcine and 1-naphthol.

[0119] The developer/-coupler combination 2,4,5,6-Tetraminopyrimidineand 2-Methylresorcine are preferred for assessing of red shades, or

[0120] p-Toluenediamine and 4-Amino-2-hydroxytoluene are preferred forassessing of blue-violet shades, or

[0121] p-Toluenediamine and 2-Amino-4-hydroxyethylaminoanisole arepreferred for assessing of blue shades, or

[0122] p-Toluenediamine and 2,4-Diamino-phenoxyethynol are preferred forassessing of blue shades, or

[0123] 3-Methyl-4-aminophenol and 4-Amino-2-hydroxytlouene are preferredfor assessing of orange shades, or

[0124] p-Toluenediamine and resorcine are preferred for assessing ofbrown-green shades, or

[0125] p-Toluenediamine and 1-Naphthol are preferred for assessing ofblue-violet shades, or

[0126] p-Toluenediamine and 2-methylresorcine are preferred forassessing of brown-gold shades.

[0127] Further, the colouring method according to the present inventionmay also contain autooxidizable compounds, such as, for example benzene,indol, or indoline, especially 5,6-dihydroxyindol or5,6-dihydroxyindoline derivatives as described in WO 99/20234,especially on page 26, line 10 to page 28, line 15, or in WO 00/28957 onpage 2, third paragraph.

[0128] Preferred autooxidizable benzene derivatives are:

[0129] 1,2,4-trihydroxybenzene, 1-methyl-2,4,5-trihydroxybenzene,2,4-diamnio-6-methylphenol, 2-amino-4-methylaminophenol,2,5-diamino-4-methyl-phenol, 2,6-diamino-4-diethylamino-phenol,2,6-diamino-1,4-dihydroxybenzen, and the salts of these compounds, whichare accessible with acid.

[0130] Preferred autooxidizable indol derivatives are:

[0131] 5,6-dihydroxyindol, 2-methyl-5,6-dihydroxyindol,3-methyl-5,6-dihydroxyindole, 1-methyl-5,6-dihydroxyindol,2,3-dimethyl-5,6-dihydroxyindol, 5-methoxy-6-dihydroxyindol,5-acetoxy-6-hydroixyindol, 5,6-diacetoxyindol, acid of5,6-dihydroxyindol-2-carbonacid, and the salts of these compounds, whichare accessible with acid.

[0132] Preferred autooxidizable indoline derivatives are:

[0133] 5,6-dihydroxyindoline, 1-methyl-5,6-dihydroxyindoline,1-ethyl-5,6-dihydroxyindoline, and the salts of these compounds, whichare accessible with acid.

[0134] The colouring method according to the present invention alsoconcerns the joint use of at least two different developers and at leastone coupler compound, or combinations of at least two different couplersand at least one developer compound. Such combinations are for exampledescribed in German Patent Application 197 172 24, especially on page 3,line 31 to page 5, line 8.

[0135] In addition, the colouring method according to the presentinvention may also contain naturally occurring dyes, such as, forexample, henna red, henna neutral, henna black, camomile blossom,sandalwood, black tea, Rhamnus frangula bark, sage, campeche wood,madder root, catechu, sedre and alkanet root. Such colouring methods aredescribed, for example, in EP-A-404 868, especially on page 3, line 55to page 4, line 9.

[0136] The present invention also describes formulations, which are usedfor the colouration of keratin fibres, especially human hair.

[0137] The formulations are applicable on human hair in differenttechnical forms. The specific technical form may be chosen in view ofthe envisaged application and/or dye or dye composition. Technical formsof formulation are for example a solution, especially a thickened wateryor watery alcoholic solution, a cream, foam, a gel, or an emulsion.

[0138] Preferred forms of formulations are ready to use compositions ora multi-compartment dyeing device or ‘kit’ or any of themulti-compartment packaging systems with compartments as described forexample as described in U.S. Pat. No. 6,190,421, column 2, lines 16 to31.

[0139] The colouring compositions for carrying out the method accordingto the invention may furthermore comprise any active ingredient,additive or adjuvant known for such preparations.

[0140] Adjuvants that are suitable for such formulations are in generalcustomary in the field hair-colouring, such as for example surfactantsor tensides, solvents, bases, acids, perfumes, polymeric adjuvant,thickeners and light stabilisers.

[0141] Suitable combinations of the colouring compositions for carryingout the method according to the invention with adjuvant used in thecolouring of hair, for example with

[0142] combination of direct dyes with oxidizing agents to achievelightened colouration; wherein oxidizing agents especially described inWO 97/20545, especially page 9, lines 5 to 9,

[0143] combination of direct dyes and/or an oxidation dye and oxidizingagents in the form of permanent-wave fixing solution, especiallyoxidizing agents as described in DE-A-19 713 698, especially page 4,lines 52 to 55, or EP-A-1 062 940, especially page 6, lines 41 to 47,(and in the equivalent WO 99/40895),

[0144] oxidation dyes in the presence of oxidoreductase enzyme, asdescribed in WO 99/17730, especially page 4, line 11 to page 13, line28, and WO 99/36034, especially pages 3 to 15,

[0145] combination of cationic dyes with polyols or polyethers; polyolsor polyethers as described in EP-A-962 219, especially page 27, lines 14to 38,

[0146] thickening polymers, as described in EP-A-970 684, especiallypage 48, line 16 to page 51, line 4,

[0147] sugar-containing polymers, as described in EP-A-970 687,especially page 28, line 17 to page 29, line 23,

[0148] quaternary ammonium salts, as described in WO 00/10517,especially page 44, line 16 to page 46, line 23,

[0149] anionic surfactants, as described in WO 00/10518, especially page45, line 11 to page 48, line 3,

[0150] non-ionic surfactants, as described in WO 00/10519, especiallypage 45, line 11 to page 50, line 12, or

[0151] silicones, as described in WO 00/12057, especially page 45, line9 to page 55, line 2.

[0152] oxidative agent or laser and direct dyes, as described in EP-920856, especially on page 2, line 31 to page 53 line 36, and on page 49,line 38 to page 50, line 41, with direct dyes as described on page 3,line 54 to page 48, line 52, or

[0153] direct dyes in the presence of cationic amphotere, substantivepolymer, as described in EP-953 334, especially on page 2, line 39 topage 7, line 44, with direct dyes as described on page 8, line 54 topage 27, line 16, and polymers as described on page 27, line 17 to page30, line 14, or

[0154] direct dyes formulations with polymer thickener on the basis ofacrylic acid, as described in EP-970 685, especially on page 2, line 39to page 10, line 1, with direct dyes as described on page 10, line 7 topage 48, line 15, with polymers as described on page 48, line 17 to page49, line 28.

[0155] The colouring composition for carrying out the method accordingto the invention in many cases comprise at least one surfactant, therebeing suitable in principle anionic and also zwitterionic, ampholytic,non-ionic and cationic surfactants. In many cases, however, it hasproved advantageous to select the surfactants from anionic, zwitterionicand non-ionic surfactants.

[0156] Anionic surfactants suitable for use in the colouringcompositions for carrying out the method according to the inventioninclude all anionic surface-active substances that are suitable for useon the human body. Such substances are characterised by an anionic groupthat imparts water solubility, for example a carboxylate, sulfate,sulfonate or phosphate group, and a lipophilic alkyl group havingapproximately from 10 to 22 carbon atoms. In addition, glycol orpolyglycol ether groups, ester, ether and amide groups and also hydroxygroups may be present in the molecule. The following are examples ofsuitable anionic surfactants, each in the form of sodium, potassium orammonium salts or mono-, di- or tri-alkanolammonium salts having 2 or 3carbon atoms in the alkanol group:

[0157] linear fatty acids having from 10 to 22 carbon atoms (soaps),

[0158] ether carboxylic acids of formula R—O—(CH₂—CH₂—O)_(x)—CH₂—COOH,in which R is a linear alkyl group having from 10 to 22 carbon atoms andx=0 or from 1 to 16,

[0159] acyl sarcosides having from 10 to 18 carbon atoms in the acylgroup,

[0160] acyl taurides having from 10 to 18 carbon atoms in the acylgroup,

[0161] acyl isothionates having from 10 to 18 carbon atoms in the acylgroup,

[0162] sulfosuccinic mono- and di-alkyl esters having from 8 to 18carbon atoms in the alkyl group and sulfosuccinic monoalkylpolyoxyethylesters having from 8 to 18 carbon atoms in the alkyl group and from 1 to6 oxyethyl groups,

[0163] linear alkane sulfonates having from 12 to 18 carbon atoms,

[0164] linear α-olefin sulfonates having from 12 to 18 carbon atoms,

[0165] α-sulfo fatty acid methyl esters of fatty acids having from 12 to18 carbon atoms,

[0166] alkyl sulfates and alkyl polyglycol ether sulfates of formulaR′-O(CH₂—CH₂—O)_(x)—SO₃H, in which R′ is a preferably linear alkyl grouphaving from 10 to 18 carbon atoms and x′=0 or from 1 to 12,

[0167] mixtures of surface-active hydroxysulfonates according to DE-A-3725 030, especially page 3, lines 40 to 55,

[0168] sulfated hydroxyalkylpolyethylene and/or hydroxyalkylenepropyleneglycol ethers according to DE-A-3 723 354, especially page 4, lines 42to 62,

[0169] sulfonates of unsaturated fatty acids having from 12 to 24 carbonatoms and from 1 to 6 double bonds according to DE-A-3 926 344,especially page 2, lines 36 to 54,

[0170] esters of tartaric acid and citric acid with alcohols which areaddition products of approximately from 2 to 15 molecules of ethyleneoxide and/or propylene oxide with fatty alcohols having from 8 to 22carbon atoms, or

[0171] anionic surfactants, as described in WO 00/10518, especially page45, line 11 to page 48, line 3.

[0172] Preferred anionic surfactants are alkyl sulfates, alkylpolyglycol ether sulfates and ether carboxylic acids having from 10 to18 carbon atoms in the alkyl group and up to 12 glycol ether groups inthe molecule, and also especially salts of saturated and especiallyunsaturated C₈-C₂₂carboxylic acids, such as oleic acid, stearic acid,isostearic acid and palmitic acid.

[0173] Surface-active compounds that carry at least one quaternaryammonium group and at least one —COO⁽⁻⁾ or —SO₃ ⁽⁻⁾ group in themolecule are termed zwitterionic surfactants. Zwitterionic surfactantsthat are especially suitable are the so-called betaines, such as theN-alkyl-N,N-dimethylammonium glycinates, for examplecocoalkyldimethylammonium glycinate,N-acylaminopropyl-N,N-dimethylammonium glycinates, for examplecocoacylaminopropyl-dimethylammonium glycinate, and2-alkyl-3-carboxymethyl-3-hydroxyethylimidazolines having from 8 to 18carbon atoms in the alkyl or acyl group and alsococoacylaminoethylhydroxyethylcarboxymethyl glycinate. A preferredzwitterionic surfactant is the fatty acid amide derivative known by theCTFA name cocoamidopropyl betaine.

[0174] Ampholytic surfactants are to be understood as meaningsurface-active compounds that, in addition to a C₈-C₁₈-alkyl or -acylgroup, contain at least one free amino group and at least one —COOH or—SO₃H group in the molecule and are capable of forming internal salts.

[0175] Examples of suitable ampholytic surfactants includeN-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids,N-alkyliminodipropionic acids,N-hydroxyethyl-N-alkylamidopropyl-glycines, N-alkyltaurines,N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoaceticacids, each having approximately from 8 to 18 carbon atoms in the alkylgroup. Ampholytic surfactants to which special preference is given areN-cocoalkyl-aminopropionate, cocoacylaminoethylaminopropionate andC₁₂-C₁₈acylsarcosine.

[0176] Non-ionic surfactants are described in WO 00/10519, especiallypage 45, line 11 to page 50, line 12.

[0177] Non-ionic surfactants contain as the hydrophilic group, forexample, a polyol group, a polyalkylene glycol ether group or acombination of polyol and polyglycol ether groups.

[0178] Such compounds are, for example:

[0179] addition products of from 2 to 30 mol of ethylene oxide and/orfrom 0 to 5 mol of propylene oxide with linear fatty alcohols havingfrom 8 to 22 carbon atoms, with fatty acids having from 12 to 22 carbonatoms and with alkylphenols having from 8 to 15 carbon atoms in thealkyl group,

[0180] C₁₂-C₂₂ fatty acid mono- and di-esters of addition products offrom 1 to 30 mol of ethylene oxide with glycerol,

[0181] C₈-C₂₂alkyl-mono- and -oligo-glycosides and ethoxylated analoguesthereof,

[0182] addition products of from 5 to 60 mol of ethylene oxide withcastor oil and hydrogenated castor oil,

[0183] addition products of ethylene oxide with sorbitan fatty acidesters,

[0184] addition products of ethylene oxide with fatty acidalkanolamides.

[0185] Examples of cationic surfactants that can be used in thecolouring compositions for carrying out the method according to theinvention are especially quaternary ammonium compounds. Preference isgiven to ammonium halides, such as alkyltrimethylammonium chlorides,dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides,for example cetyltrimethylammonium chloride, stearyltrimethylammoniumchloride, distearyidimethylammonium chloride, lauryldimethylammoniumchloride, lauryidimethylbenzylammonium chloride andtricetylmethylammonium chloride. Further cationic surfactants that canbe used in accordance with the invention are quaternised proteinhydrolysates.

[0186] Also suitable in accordance with the invention are cationicsilicone oils, such as, for example, the commercially available productsQ2-7224 (manufacturer: Dow Corning; a stabilisedtrimethylsilylamodimethicone), Dow Corning 929 emulsion (comprising ahydroxylamino-modified silicone, which is also referred to asamodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067(manufacturer: Wacker) and also Abil®-Quat 3270 and 3272 (manufacturer:Th. Goldschmidt; diquaternary polydimethylsiloxanes, quaternium-80), orsilicones, as described in WO 00/12057, especially page 45, line 9 topage 55, line 2.

[0187] Alkylamidoamines, especially fatty acid amidoamines, such as thestearylamidopropyl-dimethylamine obtainable under the name Tego Amid®18, are distinguished not only by a good conditioning action but alsoespecially by their good biodegradability.

[0188] Quaternary ester compounds, so-called “esterquats”, such as themethyl hydroxyalkyl-dialkoyloxyalkylammonium methosulfates marketedunder the trademark Stepantex®, are also very readily biodegradable.

[0189] An example of a quaternary sugar derivative that can be used ascationic surfactant is the commercial product Glucquat®100, according toCTFA nomenclature a “lauryl methyl gluceth-10 hydroxypropyl dimoniumchloride”.

[0190] The alkyl-group-containing compounds used as surfactants may besingle substances, but the use of natural raw materials of vegetable oranimal origin is generally preferred in the preparation of suchsubstances, with the result that the substance mixtures obtained havedifferent alkyl chain lengths according to the particular startingmaterial used.

[0191] The surfactants that are addition products of ethylene and/orpropylene oxide with fatty alcohols or derivatives of such additionproducts may either be products having a “normal” homologue distributionor products having a restricted homologue distribution. “Normal”homologue distribution is to be understood as meaning mixtures ofhomologues obtained in the reaction of fatty alcohol and alkylene oxideusing alkali metals, alkali metal hydroxides or alkali metal alcoholatesas catalysts. Restricted homologue distributions, on the other hand, areobtained when, for example, hydrotalcites, alkali metal salts of ethercarboxylic acids, alkali metal oxides, hydroxides or alcoholates areused as catalysts. The use of products having restricted homologuedistribution may be preferred.

[0192] Examples of further active ingredients, adjuvants and additivesare as follows:

[0193] non-ionic polymers, for example vinylpyrrolidone/vinyl acrylatecopolymers, polyvinyl-pyrrolidone and vinylpyrrolidone/vinyl acetatecopolymers and polysiloxanes,

[0194] cationic polymers, such as quaternised cellulose ethers,polysiloxanes having quaternary groups, dimethyldiallylammonium chloridepolymers, copolymers of dimethyldiallylammonium chloride and acrylicacid, as available commercially under the name Merquat® 280 and the useof which in hair colouring is described, for example, in DE-A-4 421 031,especially page 2, lines 20 to 49, or EP-A-953 334, especially page 27,line 17 to page 30, line 11, acrylamide/dimethyldiallylammonium chloridecopolymers, diethyl-sulfate-quaternised dimethylaminoethylmethacrylate/vinylpyrrolidone copolymers, vinylpyrrolidone/imidazoliniummethochloride copolymers,

[0195] quaternised polyvinyl alcohol,

[0196] zwitterionic and amphoteric polymers, such as, for example,acrylamido-propyl-trimethylammonium chloride/acrylate copolymers andoctylacrylamide/methyl methacrylate/tert-butylaminoethylmethacrylate/2-hydroxypropyl methacrylate copolymers,

[0197] anionic polymers, such as, for example, polyacrylic acids,crosslinked polyacrylic acids, vinyl acetate/crotonic acid copolymers,vinylpyrrolidone/vinyl acrylate copolymers, vinyl acetate/butylmaleate/isobornyl acrylate copolymers, methyl vinyl ether/maleicanhydride copolymers and acrylic acid/ethyl acrylate/N-tert-butylacrylamide terpolymers,

[0198] thickeners, such as agar, guar gum, alginates, xanthan gum, gumarabic, karaya gum, locust bean flour, linseed gums, dextrans, cellulosederivatives, e.g. methyl cellulose, hydroxyalkyl cellulose andcarboxymethyl cellulose, starch fractions and derivatives, such amylose,amylopectin and dextrins, clays, e.g. bentonite or fully synthetichydrocolloids such as, for example, polyvinyl alcohol,

[0199] structuring agents, such as glucose and maleic acid,

[0200] hair-conditioning compounds, such as phospholipids, for examplesoya lecithin, egg lecithin, and cephalins, silicone oils, and alsoconditioning compounds, for example such as those described in DE-A-19729 080, especially page 2, lines 20 to 49, EP-A-834 303, especiallypage 2, line 18 to page 3, line 2, or EP-A-312 343, especially page 2,line 59 to page 3, line 11,

[0201] protein hydrolysates, especially elastin, collagen, keratin, milkprotein, soya protein and wheat protein hydrolysates, condensationproducts thereof with fatty acids and also quaternised proteinhydrolysates,

[0202] perfume oils, dimethyl isosorbitol and cyclodextrins,

[0203] solubilisers, such as ethanol, isopropanol, ethylene glycol,propylene glycol, glycerol and diethylene glycol,

[0204] anti-dandruff active ingredients, such as piroctones, olaminesand zinc Omadine,

[0205] further substances for adjusting the pH value,

[0206] active ingredients such as panthenol, pantothenic acid,allantoin, pyrrolidonecarboxylic acids and salts thereof, plant extractsand vitamins,

[0207] cholesterol,

[0208] light stabilisers and UV absorbers, as described, for example, inEP-A-819 422, especially page 4, lines 34 to 37,

[0209] consistency regulators, such as sugar esters, polyol esters orpolyol alkyl ethers,

[0210] fats and waxes, such as spermaceti, beeswax, montan wax,paraffins, fatty alcohols and fatty acid esters,

[0211] fatty alkanolamides,

[0212] polyethylene glycols and polypropylene glycols having a molecularweight of from 150 to 50 000, for example such as those described inEP-A-801 942, especially page 3, lines 44 to 55,

[0213] complexing agents, such as EDTA, NTA and phosphonic acids,

[0214] swelling and penetration substances, such as polyols and polyolethers, as listed extensively, for example, in EP-A-962 219, especiallypage 27, lines 18 to 38, for example glycerol, propylene glycol,propylene glycol monoethyl ether, butyl glycol, benzyl alcohol,carbonates, hydrogen carbonates, guanidines, ureas and also primary,secondary and tertiary phosphates, imidazoles, tannins, pyrrole,

[0215] opacifiers, such as latex,

[0216] pearlising agents, such as ethylene glycol mono- and di-stearate,

[0217] propellants, such as propane-butane mixtures, N₂O, dimethylether, CO₂ and air, and also

[0218] antioxidants,

[0219] polyols or polyethers, as described in EP-A-962 219, especiallypage 27, lines 14 to 38,

[0220] thickening polymers, as described in EP-A-970 684, especiallypage 48, line 16 to page 51, line 4,

[0221] sugar-containing polymers, as described in EP-A-970 687,especially page 28, line 17 to page 29, line 23,

[0222] quaternary ammonium salts, as described in WO 00/10517,especially page 44, line 16 to page 46, line 23.

[0223] In the context of the present invention, oxidizing agents areunderstood to be any oxidizing agent customarily used for oxidative haircolouring, for example dilute hydrogen peroxide solutions, hydrogenperoxide emulsions or hydrogen peroxide gels, alkaline earth metalperoxides, organic peroxides, such as urea peroxides, melamineperoxides, or alkalimetalbromat fixations are also applicable if ashading powder on the basis of semi-permanent, direct hair dyes is used.

[0224] Preferred oxidizing agent is hydrogen peroxide, preferred inabout 2 to 30% by weight, more preferred in 3 to 20% by weight, and mostpreferred in 6 to 12% by weight of the total weight of a waterycomposition such as a solution, dispersion, a gel or emulsion.

[0225] The watery composition can comprise all customary components,which are used for the different applications of oxidizing agentcompositions as described in K. Schrader, “Grundlagen und Rezepturen derKosmetika”, 2. Aufl. (1989), page 832-840.

[0226] Further preferred oxidizing agents are

[0227] oxidizing agents to achieve lightened colouration, as describedin WO 97/20545, especially page 9, lines 5 to 9,

[0228] oxidizing agents in the form of permanent-wave fixing solution,as described in DE-A-19 713 698, especially page 4, lines 52 to 55, andlines 60 and 61 or EP-A-1 062 940, especially page 6, lines 41 to 47,(and in the equivalent WO 99/40895).

[0229] An oxidizing agent may be present in the colouring compositionsfor carrying out the method according to the invention preferably in anamount of from 0.01% to 6%, especially from 0.01% to 1%, based on thetotal dyeing composition.

[0230] Preferred catalysts are metal ions, such as for example Zn²⁺,Cu²⁺, Fe²⁺, Fe³⁺, Mn²⁺, Mn⁴⁺, Li⁺, Mg²⁺, Ca²⁺ and Al³⁺, preferably Zn²⁺,Cu²⁺ and Mn²⁺.

[0231] The metal ions are applicable in any physiological suitable saltsform. Preferred salts are acetate, sulfate, halogenide, lactate andtartrate.

[0232] Alkalimetalsulfits, such as sodium-, potassium-, lithium-sulfite,Alkalimetaldisulfits, such as sodium-, potassium-, lithium-disulfite,ascorbic acid, tert.-Butylhydrochinon and Ammoniumthiolactat.

[0233] In general, the coloration with an oxidative agent is conductedin the presence of a base. Bases are for example ammonia, alkali metalcarbonates, earth metal carbonates, alkanol amines, such as for examplemono-, di- or triethanolamine, alkali metal hydroxides, earth metalhydroxides, compounds of the formula

[0234] wherein,

[0235] R is a propyl residue, which substituted with OH or C₁-C₄-alkyl,

[0236] R₃, R₄, R₅ and R₆ are independently or dependently from eachother hydrogen, C₁-C₄-alkyl or hydroxy-(C₁-C₄)-alkyl.

[0237] Alkali metal is for example sodium, potassium or lithium.

[0238] Earth metal is for example magnesium or calcium.

[0239] Acids are inorganic or organic acids, such as hydrochloride,tartrat acid, citric acid, ascorbine acid and phosphor acid.

[0240] The use of UV absorbers can effectively protect natural and dyedhair from the damaging rays of the sun and increase the wash fastness ofdyed hair.

[0241] Suitable UV absorbers the colouring compositions for carrying outthe method according to the invention are:

[0242] cationic benzotriazole UV absorbers as for example described inWO 01/36396 especially on page 1, line 20 to page 2, line 24, andpreferred on page 3 to 5, and on pages 26 to 37, or

[0243] cationic benzotriazole UV in combination with antioxidants asdescribed in WO 01/36396, especially on page 11, line 14 to page 18, or

[0244] UV absorbers in combination with antioxidants as described inU.S. Pat. No. 5,922,310, especially in column 2, lines 1 to 3,

[0245] UV absorbers in combination with antioxidants as described inU.S. Pat. No. 4,786,493, especially in column 1, 42 to column 2, line 7,and preferred in column 3, 43 to column 5, line 20, or

[0246] combination of UV absorbers as described in U.S. Pat. No.5,830,441, especially in column 4, lines 53 to 56, or

[0247] combination of UV absorbers as described in WO 01/36396,especially on page 11, lines 9 to 13, or

[0248] triazine derivatives provide effective UV protection as describedin WO 98/22447, especially on page 1, line 23 to page 2, line 4, andpreferred on page 2, line 11 to page 3, line 15 and most preferred onpages 6 to 7, and 12 to 16, or

[0249] combination of the cosmetic formulations as described in WO98/22447 with one or more than one further UV filter as described in thefollowing patents:

[0250] (Abbreviations T: table, R: row, Comp: compound, Ex: compound(s)of patent example, p=page; pp=pages) EP 895776 Comp. in Rows 48-58, p 3;R 25 + 33, p 5 WO 9220690 Polymeric comp in Examples 3-6 EP 1000950Comp. in Table 1, pp 18-21 EP 1060734 T 1-3, pp 11-14 EP 1059082 Ex 1; T1, pp 9-11 EP 1008586 Ex 1-3, pp 13-15 EP 1005855 T 3, p 13 EP 1129695Ex 1-7, pp 13-14 EP 967200 Ex 2; T 3-5, pp 17-20 EP 945125 T 3 a + b, pp14-15 EP 924246 T 2, p 9 EP 911020 T 2, p 11-12 EP 916335 T 2-4, pp19-41 EP 852137 T 2, pp 41-46 EP 858318 T 1, p 6 EP 826361 T 1, pp 5-6EP 503338 T 1, pp 9-10 WO 9301164 T 1 + 2, pp 13-22 EP 823418 Ex 1-4, pp7-8 WO 9714680 Ex 1-3, p 10 EP 1027883 Compound VII, p 3 EP 832641 Ex5 + 6 p 7; t 2, p 8 U.S. Pat. No. 5338539 Ex 1-9, pp 3 + 4 EP 517103 Ex3, 4, 9, 10 pp 6-7 EP 1123934 T 3, p 10 EP 1027883 Comp I-VI, p 3 EP969004 Ex 5, T 1, pp 6-8 U.S. Pat. No. 5801244 Ex 1-5, pp 6-7 EP 832642Ex 22, T 3 pp, 10-15; T 4, p 16 U.S. Pat. No. 5346691 (EP 570838) Ex 40,p 7; T 5, p 8 EP 517104 Ex 1, T 1, pp 4-5; Ex 8, T 2, pp 6-8 WO200149686 Ex 1-5, pp 16-21 EP 944624 Ex 1 + 2, pp 13-15 EP 933376 Ex1-15, pp 10-21 EP 863145 Ex 1-11, pp 12-18 EP 780382 Ex 1-11, pp 5-7 EP626950 all examples EP 1081140 Ex 1-9, pp 11-16 WO 9217461 Ex 1-22, pp10-20 WO 0168047 Tables on pp 85-96 EP 613893 Ex 1-5 + 15, T 1, pp 6-8EP 1064922 Compounds 1-34, pp 6-14 EP 1028120 Ex 1-5, pp 5-13 EP 1008593Ex 1-8, pp 4-5 EP 669323 Ex 1-3, p 5 EP 1108712 4,5-Dimorpholino-3-hydroxypyridazine JP 2000319629 CAS Regno. 80142-49-0, 137215-83-9,307947-82-6 EP 420707 B1 Ex 3, p 13 (80142-49-0) U.S. Pat. No. 5635343all examples EP 1167358 all examples

[0251] In addition to the triazine UV absorbers described in WO98/22447, the cosmetic formulations can also contain one or more thanone further UV protective of the following substance classes:

[0252] p-aminobenzoic acid derivatives, for example4-dimethylaminobenzoic acid 2-ethylhexyl ester;

[0253] salicylic acid derivatives, for example salicylic acid2-ethylhexyl ester;

[0254] benzophenone derivatives, for example2-hydroxy-4-methoxybenzophenone and its 5-sulfonic acid derivative;

[0255] dibenzoylmethane derivatives, for example1-(4-tert-butylphenyl)-3-(4-methoxyphenyl)-propane-1,3-dione;

[0256] diphenylacrylates, for example 2-ethylhexyl2-cyano-3,3-diphenylacrylate, and 3-(benzofuranyl) 2-cyanoacrylate;

[0257] 3-imidazol-4-ylacrylic acid and esters;

[0258] benzofuran derivatives, especially 2-(p-aminophenyl)benzofuranderivatives, described in EP-A-582 189, U.S. Pat. No. 5,338,539, U.S.Pat. No. 5,518,713 and EP-A-613 893;

[0259] polymeric UV absorbers, for example the benzylidene malonatederivatives described in EP-A-709 080;

[0260] cinnamic acid derivatives, for example the 4-methoxycinnamic acid2-ethylhexyl ester and isoamyl ester or cinnamic acid derivativesdescribed in U.S. Pat. No. 5,601,811 and WO 97/00851;

[0261] camphor derivatives, for example3-(4′-methyl)benzylidene-bornan-2-one, 3-benzylidenebornan-2-one,N-[2(and 4)-2-oxyborn-3-ylidene-methyl)-benzyl]acrylamide polymer,3-(4′-trimethylammonium)-benzylidene-bornan-2-one methyl sulfate,3,3′-(1,4-phenylenedimethine)-bis(7,7-dimethyl-2-oxo-bicyclo[2.2.1]heptane-1-methanesulfonicacid) and salts, 3-(4′-sulfo)benzylidene-bornan-2-one and salts;camphorbenzalkonium methosulfate;

[0262] hydroxyphenyltriazine compounds, for example2-(4′-methoxyphenyl)-4,6-bis(2′-hydroxy-4′-n-octyloxyphenyl)-1,3,5-triazine;2,4-bis{[4-(3-(2-propyloxy)-2-hydroxy-propyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine;2,4-bis{[4-(2-ethyl-hexyloxy)-2-hydroxy]-phenyl}-6-[4-(2-methoxyethyl-carboxyl)-phenylamino]-1,3,5-triazine;2,4-bis{[4-(tris(trimethylsilyloxy-silylpropyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine;0,2,4-bis{[4-(2″-methylpropenyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine;2,4-bis{[4-(1′,1′,1′,3′,5′,5′,5′-heptamethyltrisilyl-2″-methyl-propyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine;2,4-bis{[4-(3-(2-propyloxy)-2-hydroxy-propyloxy)-2-hydroxy]-phenyl}-6-[4-ethylcarboxy)-phenylamino]-1,3,5-triazine;

[0263] benzotriazole compounds, for example2,2′-methylene-bis(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)-phenol;

[0264] trianilino-s-triazine derivatives, for example2,4,6-trianiline-(p-carbo-2′-ethyl-1′-oxy)-1,3,5-triazine and the UVabsorbers disclosed in U.S. Pat. No. 5,332,568, EP-A-517 104, EP-A-507691, WO 93/17002 and EP-A-570 838;

[0265] 2-phenylbenzimidazole-5-sulfonic acid and salts thereof; methylo-aminobenzoates;

[0266] physical sunscreens coated or not as titanium dioxide, zincoxide, iron oxides, mica, MnO, Fe₂O₃, Ce₂O₃, Al₂O₃, ZrO₂. (surfacecoatings: polymethylmethacrylate, methicone (methylhydrogenpolysiloxaneCAS 9004-73-3), dimethicone, isopropyl titanium triisostearate (CAS61417-49-0), metal soaps as magnesium stearate (CAS 4086-70-8),perfluoroalcohol phosphate as C₉₋₁₅ fluoroalcohol phosphate (CAS74499-44-8; JP 5-86984, JP 4-330007)). The primary particle size is anaverage of 15 nm-35 nm and the particle size in dispersion is in therange of 100 nm-300 nm.

[0267] aminohydroxy-benzophenone derivatives disclosed in DE 10011317,EP 1133980 and EP 1046391

[0268] phenyl-benzimidazole derivatives as disclosed in EP 1167358

[0269] The UV absorbers described in “Sunscreens”, Eds. N. J. Lowe, N.A. Shaath, Marcel Dekker, Inc., New York and Basle or in Cosmetics &Toiletries (i 07), 50ff (1992) also can be used as additional UVprotective substances.

[0270] Examples of (synergistic) combinations of UV absorbers inpreparations are also described in the following table. The combinationsof UV filters are useful to protect hair and/or natural or artificialhair color (ratio of UV absorbers in columns C1-C12). No Chemical NameCAS No. C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 C11 C12 UV 1(+/−)-1,7,7-trimethyl-3- 36861-47-9 15 [(4-methylphenyl)-methylene]bicyclo [2.2.1]heptan-2-one UV 2 1,7,7-trimethyl-3- 15087-24-85 (phenylmethylene)- bicyclo[2.2.1]heptan-2- one UV 3 (2-Hydroxy-4-1641-17-4 10 methoxyphenyl)(4- methylphenyl) methanone UV 42,4-dihydroxybenzophenone 131-56-6 10 UV 5 2,2′,4,4′- 131-55-5 10tetrahydroxybenzophenone UV 6 2-Hydroxy-4- 131-57-7 methoxybenzophenone;UV 7 2-Hydroxy-4- 4065-45-6 5 methoxybenzophenone- 5-sulfonic acid UV 82,2′-dihydroxy-4,4′- 131-54-4 10 10 dimethoxybenzophenone UV 92,2′-Dihydroxy-4- 131-53-3 10 methoxybenzophenone UV 10Alpha-(2-oxoborn-3- 56039-58-8 15 10 10 ylidene)toluene-4- sulphonicacid and its salts UV 11 1-[4-(1,1- 70356-09-1 10 10dimethylethyl)phenyl]- 3-(4-methoxyphenyl)- propane-1,3-dione UV 12Methyl N,N,N- 52793-97-2 trimethyl-4-[(4,7,7- trimethyl-3-oxobicyclo[2,2,1]hept- 2-ylidene)methyl]- anilinium sulphate; UV 223,3,5-Trimethylcyclohexyl- 118-56-9 5 2-hydroxybenzoate UV 23 Isopentylp-methoxycinnamate 71617-10-2 10 UV 27 Menthyl-o- 134-09-8 5aminobenzoate UV 28 Methyl salicylate 89-46-3 10 UV 29 2-Ethylhexyl 2-6197-30-4 15 10 cyano,3,3- diphenylacrylate UV 30 2-ethylhexyl 4-21245-02-3 5 (dimethyl- amino)benzoate UV 31 2-ethylhexyl 4- 5466-77-320 20 50 methoxycinnamate UV 32 2-ethylhexyl salicylate 118-60-5 UV 33Benzoic acid,4,4′,4″- 88122-99-0 10 10 (1,3,5-triazine-2,4,6-triyltri-imino)tris-, tris(2-ethylhexyl) ester; 2,4,6-Trianilino-(p-carbo-2′-ethylhexyl- 1′-oxi)-1,3,5-triazine UV 34 4-aminobenzoic acid150-13-0 5 UV 35 Benzoic acid, 4- 113010-52-9 amino-, ethyl ester,polymer with oxirane UV 38 2-phenyl-1H- 27503-81-7 10 10 10benzimidazole-5- sulphonic acid UV 39 2-Propenamide, N-[[4- 147897-12-95 [(4,7,7-trimethyl-3- oxobicyclo-[2.2.1]hept- 2-ylidene)methyl]-phenyl]methyl]-, homopolymer UV 40 Triethanolamine 2174-16-5 5salicylate UV 41 3,3′-(1,4-phenylene- 90457-82-2 5 dimethylene)bis[7,7-dimethyl-2-oxobicyclo [2.2.1]heptane- 1-methanesulfonic acid] UV 42Titanium dioxide 13463-67-7 5 7.5 20 5 10 UV 44 Zinc oxide 1314-13-2 1010 10 UV 45 2,2′-Methylene-bis-[6- 103597-45-1 15 20 20 10 10(2H-benzotriazol-2-yl)- 4-(1,1,3,3-tetramethyl- butyl)-phenol] UV 462,4-bis{[4-(2-ethylhexyloxy)- 187393-00-6 10 15 15 15 10 2-hydroxy]-phenyl}-6-(4-methoxyphenyl)- (1,3,5)-triazine UV 47 1H-Benzimidazole-180898-37-7 15 10 4,6-disulfonic acid, 2,2′-(1,4- phenylene)bis-,disodium salt UV 48 Benzoic acid, 4,4′-[[6- 154702-15-5 20 15 10 10[[4-[[(1,1-dimethylethyl) amino]carbonyl]- phenyl]amino]1,3,5-triazine-2,4- diyl]diimino]bis-, bis(2- ethylhexyl)ester UV 49 Phenol,2-(2H-benzotriazol- 155633-54-8 15 15 10 10 2-yl)-4-methyl-6-[2-methyl-3-(1,3,3,3- tetramethyl-1- [(trimethylsilyl)oxy]-disiloxany]propyl]- UV 50 alpha-(trimethylsilyl)- 207574-74-1 15 15 10omega-(trimethylsilyloxy) poly[oxy(dimethyl) silylene]-co-[oxy(methyl)(2-{p-[2,2- bis(ethoxycarbonyl) vinyl]phenoxy }-1-methyleneethyl)silylene]- co-[oxy(methyl)(2- {p-[2,2-bis(ethoxycarbonyl)vinyl] phenoxy}prop-1- enyl)silylene] UV 51Benzenesulfonic acid, 92484-48-5 10 3-(2H-benzotriazol-2-yl)-4-hydroxy-5-(1- methy-lpropyl)-, monosodium salt UV 52 Benzoic acid,2-[4- 302776-68-7 35 25 15 15 30 10 10 25 10 (diethylamino)-2-hydroxybenzoyl]-, hexyl ester UV 53 1-Dodecanaminium, 156679-41-3 5N-[3-[[4- (dimethylamino)benzoyl] amino]propyl]-N,N- dimethyl-, saltwith 4- methylbenzenesulfonic acid (1:1) UV 54 1-Propanaminium,177190-98-6 5 N,N,N-trimethyl-3-[(1- oxo-3-phenyl-2- propenyl)amino]-,chloride UV 55 1H-Benzimidazole- 170864-82-1 10 10 10 10 4,6-disulfonicacid, 2,2′-(1,4- phenylene)bis- UV 56 1,3,5-Triazine, 2,4,6- 7753-12-010 7.5 15 10 5 50 15 20 20 10 10 10 tris(4-methoxyphenyl)- UV 571,3,5-Triazine, 2,4,6- 208114-14-1 10 15 5 tris[4-[(2-ethylhexyl)oxy]phenyl]- UV 58 1-Propanaminium, 3- 340964-15-0 5[[3-[3-(2H- benzotriazol-2-yl)-5- (1,1-dimethylethyl)-4-hydroxyphenyl]-1- oxopropyl]amino]-N,N- diethyl-N-methyl-, methylsulfate (salt) UV 59 2-Propenoic acid, 3- 104-98-3 5 5(1H-imidazol-4-yl)- UV 60 Benzoic acid, 2- 94134-93-7 5 hydroxy-, [4-(1-methylethyl)phenyl]methyl ester UV 61 1,2,3-Propanetriol, 1- 136-44-7 5(4-aminobenzoate) UV 62 Benzeneacetic acid, 4732-70-1 53,4-dimethoxy-a-oxo- UV 63 2-Propenoic acid, 2- 5232-99-5 5cyano-3,3-diphenyl-, ethyl ester

[0271] The following examples C1-C12 illustrate combinations of UVabsorbers and antioxidants in cosmetic preparations which are useful toprotect hair and natural or artificial hair color (% by weight, based onthe total weight of the composition). Compound (CAS No.) C1 C2 C3 C4 C5C6 C7 C8 C9 C10

2 3 4 1 2 3 1 2 2.5 1 Benzenesulfonic acid, 3-(2H-benzo- 1 1triazol-2-yl)-4-hydroxy-5-(1-meth- y-lpropyl)-, monosodium salt(92484-48-5) Propyl gallate (121-79-9) 1 0.5 1 1N-[3-(3,5-Di-tert-butyl-4-hy- 2 1 1 2 droxyphenyl)propyionyl]sulfanilcacid (or salts e.g. with sodium) Benzylidene malonate 2 0.2 polysiloxane(207574-74-1) Drometriazole trisiloxane (155633-54-8) 1 0.5Dieethylhexyl butamido triazone 0.2 (154702-15-5) Phenol,2,2′-[6-(4-meth- 0.2 oxyphenyl)-1,3,5-triazine-2,4-diyl]bis[5-[(2-eth-ylhexyl)oxy]-(187393-00-6) 1H-Benzimidazole-4,6-disulfonic 1 acid,2,2′-(1,4-phenylene)bis-, disodium salt (180898-37-7) Bis-Benzotriazolyl0.5 Tetramethylbutyl-phenol (103597-45-1) Terephthalylidene Dicamphor0.5 sulfonic acid (90457-82-2) Polyacrylamidomethyl 1 benzylidenecamphor CAMPHOR (113783-61-2) Phenylbenzimidazole sulfonic 1 acid(27503-81-7) Ethylhexyl methoxy-cinnamate 0.5 0.5 0.2 0.5 (5466-77-3)Octocrylene (6197-30-4) 0.5 0.5 Camphor benzalkonium 0.5 0.1methosulfate (52793-97-2) Butylmethoxydibenzoylmethane 1 (70356-09-1)Benzophenone-3 (131-57-7) 0.1 0.1 0.5 0.2 Benzophenone-4 (4065-45-6) 0.10.1 0.5 1-Dodecanaminium, N-[3-[[4-(di- 1methylamino)-benzoyl]amino]pro- pyl]-N,N-dimethyl-, salt with 4-meth-ylbenzenesulfonic acid (156679-41-3) 1 1 1-Propanaminium, N,N,N-tri-methyl-3-[(1-oxo-3-phenyl-2-pro- penyl)amino]-, chloride (177190-98-6)3-Benzylidene camphor (15087-24-8) 0.5 4-Methylbenziylidene camphor 0.2(36861-47-9) Benzylidene camphor sulfonic 1 acid (56039-58-8)

[0272] Preference is given to the use of mixing ratios of triazinederivatives of formula 1-8/further light-protective agents from 1:99 to99:1, especially from 1:95 to 95:1 and preferably from 10:90 to 90:10,based on weight. Of special interest are mixing ratios of from 20:80 to80:20, especially from 40:60 to 60:40 and preferably approximately50:50. Such mixtures can be used, inter alia, to improve solubility orincrease UV absorption.

[0273] Synergistic effects are observed when UV absorbers are used incombination with antioxidants. Examples of antioxidants that can be usedare listened in WO 01/36396 (pages 11-18), U.S. Pat. No. 5,922,310 andU.S. Pat. No. 4,786,493.

[0274] Examples of UV absorbers used in addition to the uncharged andcationic benzotriazole UV absorbers in the formulations withoutlimitation to those listed in the following might be benzophenone-typesubstances such as benzophenone-1, benzophenone-2, benzophenone-3,benzophenone-4, benzophenone-5 (sodium salt) or benzotriazol-typesubstances such as benzenesulfonic acid,3-(2H-benzotriazol-2-yl)-4-hydroxy-5-(1-methylpropyl)-, monosodium salt;2-(5-chloro-2H-benzotriazol-2-yl)-6-(1,1-dimethylethyl)-4-methyl-phenol;2-(2H-benzotriazol-2-yl)-6-dodecyl-4-methyl-phenol, branched and linear.Typical ingredients in the oil phase of emulsions (water in oil, oil inwater or triple emulsion) or used in hair oils can be chosen from thefollowing substance groups without limiting the kind of lipophilicingredients to those substances:

[0275] Suitable cosmetic preparations may contain usually from 0.05 to40% by weight, preferably from 0.1 to 20% by weight, based on the totalweight of the composition, of one or more UV absorbers.

[0276] Preferred are the cosmetic preparations contain at least onetriazine derivative UV absorber, for example, from 0.1 to 40% by weight,preferably from 0.1 to 20% by weight and especially from 0.5 to 10% byweight, based on the total weight of the composition, and the cosmeticpreparations contain at least one cationic benzotriazole from 0.05-20%by weight, preferred from 0.1-20% by weight, based on the total weightof the composition. Typical cosmetic formulations containing unchargedand/or cationic benzotriazoles and/or antioxidants alone or incombinations are rinse-off products (e.g. shampoos, hair rinses,conditioners etc.),

[0277] Suitable cosmetic formulations are:

[0278] cosmetic hair-treatment preparations, e.g. hair-washingpreparations in the form of shampoos and conditioners, hair-carepreparations, e.g. pre-treatment preparations or leave-on products suchas sprays, creams, gels, lotions, mousses and oils, or hair tonics,styling creams, styling gels, pomades, hair rinses, treatment packs,intensive hair treatments, hair-structuring preparations, e.g.hair-waving preparations for permanent waves (hot wave, mild wave, coldwave), hair-straightening preparations, liquid hair-settingpreparations, hair foams, hairsprays, bleaching preparations, e.g.hydrogen peroxide solutions, lightening shampoos, bleaching creams,bleaching powders, bleaching pastes or oils, temporary, semi-permanentor permanent hair colourants, preparations containing self-oxidisingdyes, or natural hair colourants, such as henna or camomile.

[0279] The final formulations listed may exist in a wide variety ofpresentation forms, for example:

[0280] in the form of liquid preparations as a W/O, O/W, O/W/O, W/O/W orPIT emulsion and all kinds of microemulsions,

[0281] in the form of a gel,

[0282] in the form of an oil, a cream, milk or lotion,

[0283] in the form of a powder, a lacquer, a tablet or make-up,

[0284] in the form of a stick,

[0285] in the form of a spray (spray with propellant gas or pump-actionspray) or an aerosol,

[0286] in the form of a foam, or

[0287] in the form of a paste.

[0288] Of special importance as cosmetic preparations for the hair arethe above-mentioned preparations for hair treatment, especiallyhair-washing preparations in the form of shampoos, hair conditioners,hair-care preparations, e.g. pre-treatment preparations, hair tonics,styling creams, styling gels, pomades, hair rinses, treatment packs,intensive hair treatments, hair-straightening preparations, liquidhair-setting preparations, hair foams and hairsprays. Of specialinterest are hair-washing preparations in the form of shampoos.

[0289] A shampoo has, for example, the following composition: from 0.01to 5% by weight of a UV absorber according to the invention, 12.0% byweight of sodium laureth-2-sulfate, 4.0% by weight of cocoamidopropylbetaine, 3.0% by weight of sodium chloride, and water ad 100%.

[0290] Any known process suitable for the preparation of microparticlescan be used for the preparation of the micronised UV absorbers, forexample:

[0291] wet-grinding with a hard grinding medium, for example zirconiumsilicate and a protective surfactant or a protective polymer in water orin a suitable organic solvent;

[0292] spray-drying from a suitable solvent, for example aqueoussuspensions or suspensions containing organic solvents, or truesolutions in water, ethanol, dichloroethane, toluene orN-methylpyrrolidone etc.;

[0293] by the expansion according to the RESS process (Rapid Expansionof Supercritical Solutions) of supercritical fluids (e.g. CO₂) in whichthe UV filter or filters is/are dissolved, or the expansion of fluidcarbon dioxide together with a solution of one or more UV filters in asuitable organic solvent;

[0294] by reprecipitation from suitable solvents, includingsupercritical fluids (GASR process=Gas Anti-SolventRecrystallisation/PCA process=Precipitation with CompressedAnti-solvents).

[0295] As grinding apparatus for the preparation of the micronisedorganic UV absorbers there may be used, for example, a jet mill, ballmill, vibratory mill or hammer mill, preferably a high-speed mixingmill. The grinding is preferably carried out with a grinding aid, forexample an alkylated vinylpyrrolidone polymer, a vinylpyrrolidone/vinylacetate copolymer, an acyl glutamate, an alkyl polyglucoside,ceteareth-25 or a phospholipid.

[0296] The micronised UV absorbers so obtained usually have an averageparticle size that is from 0.02 to 2 μm, preferably from 0.05 to 1.5 μm,and more especially from 0.1 to 1.0 μm.

[0297] The UV absorbers can also be used dry in powder form. For thatpurpose the UV absorbers are subjected to known grinding methods, suchas vacuum atomization, countercurrent spray-drying etc. Such powdershave a particle size of from 0.1 μm to 2 μm. To avoid the occurrence ofagglomeration, the UV absorbers can be coated with a surface-activecompound prior to the pulverisation process, for example with ananionic, non-ionic or amphoteric surfactant, e.g. a phospholipid or aknown polymer, such as PVP, or an acrylate. The colouring compositionsfor carrying out the method according to the invention may furthercomprise antimicrobial agents.

[0298] Typical antimicrobial preservatives and antimicrobial activesused in formulations (in most cases the INCI name of the antimicrobialsubstances is mentioned):

[0299] formaldehyde and paraformaldehyde, hydroxy biphenyls and itssalts such as ortho-phenylphenol, zinc pyrithion, chlorobutanol, hydroxybenzoic acids and their salts and esters such as methyl paraben, ethylparaben, propyl paraben, butyl paraben, dibromo hexamidine and its saltsincluding isothionate (4,4′-hexamethylenedioxy-bis(3-bromo-benzamidine)and 4,4′-hexamethylenedioxy-bis(3-bromo-benzamidinium2-hydroxyethanesulfonate), mercury, (aceto-O)phenyl (especially phenylmercuric acetate) and Mercurate(2-),(orthoborate(3-)-O)phenyl,dihydrogene (especially phenyl mercuric borate),1,3-bis(2-ethylhexyl)-hexahydro-5-methyl-5-pyrimidine (Hexetidin),5-bromo-5-nitro-1,3-dioxan, 2-bromo-2-nitro-1,3-propandiol,2,4-dichlorobenzyl alcohol, 3,4,4′ trichlorocarbanilide(Trichlorcarban), p-chloro-m-cresol, 2,4,4′-trichloro 2-hydroxydiphenylether (triclosan), 4,4′-dichloro 2-hydroxy diphenylether,4-chloro-3,5-dimethylphenol (Chloroxylenol), imidazolidinyl urea,poly-(hexamethylene biguanide)hydrochloride, 2-phenoxy ethanol(phenoxyethanol), hexamethylene tetramine(Methenamine),1-(3-chloroallyl)-3,5,7-triaza-1-azoniaadamantanchloride (Quatemium 15),1-(4-chlorophenyoxy)-1-(1-imidazolyl)3,3-dimethyl-2-butanone(Climbazole), 1,3-bis(hydroxymethyl)-5,5-dimethyl-2,4-imidazolidinedione(DMDM hydantoin), benzyl alcohol, 1,2-dibromo-2,4-dicyano butane, 2,2′methylene-bis(6-bromo-4-chloro phenol) (bromochlorophene),methylchloroisothiazolone, methylisothiazolone, octylisothiazolone,benzylisothiazolone, 2-benzyl-4-chlorophenol (Chlorophenone),chloracetamide, chlorhexidine, chlorhexidine acetate, chlorhexidinegluconate, chlorhexidine hydrochloride, 1-phenoxy-propane-2-ol(phenoxyisopropanol), 4,4-dimethyl-1,3-oxazolidine (dimethyloxazolidine), diazolidinyl urea, 4,4′-hexamethylenedioxybisbenzamidineand 4,4′-hexamethylenedioxybis(benzamidinium-2-hydroxyethanesulfonate),glutaraldehyde (1,5-pentanedial), 7-ethylbicyclooxazolidine,3-(4-chlorophenoxy)-1,2-propandiol (chlorophenesin), phenylmethoxymethanol and ((phenylmethoxy)methoxy)-methanol (benzylhemiformal),N-alkyl(C12-C₂₋₂)trimethyl ammoniumbromide and -chloride (cetrimoniumbromide, cetrimonium chloride),benzyl-dimethyl-(4-(2-(4-(1,1,3,3-tetramethylbutyl)-phenoxy)-ethoxy)-ethyl)-ammoniumchloride(benzethonium chloride), Alkyl-(C8-C₁₈)-dimethyl-benzylammoniumchloride, -bromide and saccharinate (benzalkonium chloride, benzalkoniumbromide, benzalkonium saccharinate), benzoic acid and its salts andesters, propionic acid and its salts, salicylic acid and its salt,sorbic acid and its salts, sodium iodiate, inorganic sulfites andbisulfites such as sodium sulfite, dehydroacetic acid, formic acid,mercurate(1-ethyl)2-mercaptobenzoate(2-)-O,S—,hydrogene (Thiomersal orThiomerosal), 10-undecylenic acid and its salts, octopirox (piroctoneolamine), sodium hydroxy methyl-aminoacetate(sodiumhydroxymethylglycinate), 3-iodo-2-propynyl butylcarbamate,10-undecylenic acid, sulfur.

[0300] Combinations with natural antimicrobials or chemically modifiednatural substances with antimicrobial activities such as chitosans andchitosan derivatives, farnesol, plant extracts such as clove oil, bluecypres oil etc. can be also used.

[0301] For use on human hair, the dyeing compositions can usually beincorporated into an aqueous cosmetic carrier. Suitable aqueous cosmeticcarriers include, for example, creams, sprays, emulsions, gels, powdersand also surfactant-containing foaming solutions, e.g. shampoos or otherpreparations, that are suitable for use on keratin-containing fibers.Such forms of use are described in detail in Research Disclosure 42448(August 1999). If necessary, it is also possible to incorporate thedyeing compositions into anhydrous carriers, as described, for example,in U.S. Pat. No. 3,369,970, especially column 1, line 70 to column 3,line 55. The dyeing compositions according to the invention are alsoexcellently suitable for the colouring method described in DE-A-3 829870 using a colouring comb or a colouring brush.

[0302] Further carriers for dying compositions are for example describedin “Dermatology”, edited by Ch. Culnan, H. Maibach, Verlag Marcel DekkerInc., New York, Basle, 1986, Vol. 7, Ch. Zviak, The Science of HairCare, chapter 7, pages 248-250, especially on page 243, line 1 to page244, line 12.

[0303] Suitable formulations of cationic dyes, which can be used in thecolouring compositions for carrying out the method according to theinvention are described for example in

[0304] in WO 95/01772, especially on page 11, line 29 to page 12, line7, or

[0305] in WO 01/66646, especially on page 7, line 1 to page 22, andpreferred from page 16, line 20 to page 22, or

[0306] direct dyes as described in DE-A-19 713 698, especially page 3,line 51 to page 4, line 29 and page 4, line 65 to page 5, line 60, or

[0307] direct dyes and oxidizing agent as described in WO 97/20545,especially on page 9, line 1 to page 11, line 4, in particular on page11, line 6 to page 13, line 19.

[0308] Preferred formulations of cationic dyes with other dyes, whichcan be used in the colouring compositions for carrying out the methodaccording to the invention, are:

[0309] combinations of Pyrazolo-[1,5-a]-pyrimidines with at least onecationic dye as described in EP 998,908, especially on page 47, line 3to page 49, line 26, and preferred on page 51, line 4 to page 52, line5, or

[0310] combinations of cationic dyes as described in FR-2788432,especially on page 53, line 1 to page 63, line 23, especially acombination of cationic dyes with Arianors in FR-2788432, especially onpages 51 to 52, or especially a combination with at least one BasicBrown 17, Basic brown 16, Basic Red 76 and Basic Red 118, and/or atleast one Basic Yellow 57, and/or at least one Basic Blue 99, or

[0311] combinations of direct dyes and/or an oxidation dye and oxidizingagents in the form of permanent-wave fixing solution, especially withdirect dyes as described in DE-A-19 713 698, especially page 4, line 65to page 35, line 59, or

[0312] combinations of cationic dyes and an oxidation dye of thedeveloper compound type and oxidizing agents as described in EP 850 638,especially on page 2, lines 3 to 12 and line 30 to page 14, and page 28,line 35 to page 30, line 20, preferred on page 30, line 25 to page 32,line 30, or

[0313] ready-to-use dyeing compositions and multicompartment device fordyeing keratin fibers comprising combinations of an extemporaneousmixture of a composition (A) containing one or more oxidation dyeprecursors and optionally one or more couplers, and of a composition(B), in powder form, containing one or more direct dye, preferablycationic, optionally dispersed in an organic pulverulent excipientand/or a mineral pulverulent excipient, and a composition (C) containingone or more oxidizing agent as described in U.S. Pat. No. 6,190,421,especially in column 2, line 20 to line 31 in column 7, line 15 tocolumn 8, line 43, and preferably in column 8, line 55 to column 9, line56, and preferably with direct dyes as described in column 5, line 30 tocolumn 7, line 14, or

[0314] a ready-to-use composition comprising, at least one oxidationbase, at least one cationic direct dye and at least one enzyme of2-electron oxidoreductase type in the presence of at least one donor forthe said enzyme as described in U.S. Pat. No. 6,228,129, especially incolumn 2, line 16 to column 25, line 55, and a multi-compartment dyeingdevice as described in column 26, lines 13 to 24, especially in column26, line 26 to column 27, line 9, or

[0315] a ready-to-use composition comprising compositions of at leastone direct cationic dye and at least one nitrated benzene dye asdescribed in WO 99/20235 especially on page 1, line 25 to page 8, line5, and on page 30, line 17 to page 34 line 25, with catonic direct dyesas described on page 8, line 12 to page 25 line 6, and amulti-compartment dyeing device as described on page 35, lines 21 to 27,especially on page 36, line 1 to page 37, or

[0316] a ready-to-use composition or a multi-compartment dyeing devicecomprising compositions of at least one direct cationic dye and at leastone autooxidisable oxidation dye, especially benzene, indol and indolinederivatives as described in WO 99/20234, especially on page 26, line 5to page 32, line 18, or

[0317] oxidation dyeing compositions of at least one direct dye and atleast one meta-Aminophenol derivative and at least one developercompound and an oxidizing agent as described in EP 850 636, especiallyon page 18, line 1 to page 22, line 11, or

[0318] oxidation dyeing compositions of at least one direct dye and atleast one developer compound selected from the group ofpara-Phenylenediamine derivatives and Bis-Phenylalkylenediamine and, andat least one coupler compound selected from the group of meta-Diphenolsand an oxidizing agent, as described in EP-A-850 637, especially on page19, line 24 to page 22, line 57,

[0319] cationic dye and e.g. a pyrazolo-(1,5-a)-pyrimidine derivatives,as described in EP 998 908, especially on page 47, line 25 to page 50,line 29, or

[0320] oxidative dye precursors (unsaturated aldehyde and couplercompounds), as described in German Patent Application 197 172 24,especially on page 3, line 36 to page 9 line 64.

[0321] Cationic dyes may be present in the colouring compositions forcarrying out the method according to the invention preferably in anamount of from 0.001% to 5%, especially from 0.01% to 1%, based on thetotal dyeing composition.

[0322] The pH value of the ready-to-use dyeing preparations is usuallyfrom 2 to 11, preferably from 5 to 10.

[0323] The constituents of the aqueous carrier are used in the colouringcompositions for carrying out the method according to the invention inthe amounts customary for that purpose; for example emulsifiers may beused in concentrations of from 0.5 to 30% by weight and thickeners inconcentrations of from 0.1 to 25% by weight of the total dyeingcomposition.

[0324] If direct dyes are used together with oxidation dyes, they may bestored separately or together.

[0325] It is preferred to store the oxidation dyes and direct dyes,which are not stable to reduction, separate

[0326] They may be stored in a liquid to paste-like preparation (aqueousor non-aqueous) or in the form of a dry powder.

[0327] When the dyes and adjuvants are stored together in a liquidpreparation, the preparation should be substantially anhydrous in orderto reduce reaction of the compounds.

[0328] When they are stored separately, the reactive components areintimately mixed with one another only immediately before use. In thecase of dry storage, before use a defined amount of hot (from 50 to 80°C.) water is usually added and a homogeneous mixture prepared.

[0329] One preferred method of applying direct dyes containingformulations on hair is by using a multi-compartment dyeing device or“kit” or any other multi-compartment packaging system, as described forexample in WO 97/20545 on page 4, line 19 to line 27.

[0330] The colouring compositions for carrying out the method accordingto the invention may combined with a suitable ready-to-use compositionfor the oxidation dyeing of keratin fibers, in particular human keratin,comprising an oxidizing agent, at least one direct dye and at least oneoxidation dye precursor, as described in U.S. Pat. No. 6,190,421, incolumn 1, line 65 to column 3, line 65, especially in column 10, line 62to column 12, line 65.

[0331] Preferably, such a ready-to-use composition is prepared accordingto a first preferred embodiment by a process which comprises apreliminary step which involves separately storing, on the one hand, acomposition (A) comprising, in a medium which is suitable for dyeing, atleast one developer compound, especially selected frompara-phenylenediamines and bis(phenyl)alkylenediamines, and theacid-addition salts thereof, at least one coupler, especially selectedfrom meta-phenylenediamines and the acid-addition salts thereof, and atleast one cationic direct dye, on the other hand, a composition (B)containing, in a medium which is suitable for dyeing, at least oneoxidizing agent and mixing them together at the time of use beforeapplying this mixture to the keratin fibers.

[0332] According to a second preferred embodiment for the preparation ofthe ready-to-use dye composition, the process includes a preliminarystep which involves separately storing, on the one hand, a composition(A) comprising, in a medium which is suitable for dyeing, at least onedeveloper compound, especially selected from para-phenylenediamines andbis(phenyl)alkylenediamines, and the acid-addition salts thereof, atleast one coupler compound, especially selected frommeta-phenylenediamines and the acid-addition salts thereof; on the otherhand, a composition (A′) comprising, in a medium which is suitable fordyeing, at least one cationic direct dye and, lastly, a composition (B)containing, in a medium which is suitable for dyeing, at least oneoxidizing agent as defined above, and mixing them together at the timeof use before applying this mixture to the keratin fibers.

[0333] The composition (A′) used according to this second variant of theprocess in accordance with the invention can optionally be in powderform, the cationic direct dye(s) in accordance with the invention itself(themselves) constituting, in this case, all of the said composition(A′) or optionally being dispersed in an organic and/or inorganicpulverulent excipient.

[0334] When it is present in the composition A′, the organic excipientcan be of synthetic or plant origin and is selected in particular fromcrosslinked and non-crosslinked synthetic polymers, polysaccharides suchas celluloses and modified or unmodified starches, as well as naturalproducts containing them such as sawdust and plant gums (guar gum, carobgum, xanthan gum, etc.).

[0335] When it is present in the composition (A′), the inorganicexcipient can contain metal oxides such as titanium oxides, aluminiumoxides, kaolin, talc, silicates, mica and silicas.

[0336] An very suitable excipient in the colouring compositions forcarrying out the method according to the invention is sawdust.

[0337] The powdered composition (A′) can also contain binders or coatingproducts in an amount which preferably does not exceed approximately 3%by weight relative to the total weight of the said composition (A′).

[0338] These binders are preferably selected from oils and liquid fattysubstances of inorganic, synthetic, animal or plant origin.

[0339] The composition (A′) may optionally also contain other adjuvants,in powdered form, in particular surfactants of any kind, hairconditioners such as, for example, cationic polymers, etc.

[0340] Another subject of the invention is a multi-compartment dyeingdevice or “kit” or any other multi-compartment packaging system, asdescribed for example in U.S. Pat. No. 6,228,129, especially in column26, lines 13 to 24, especially in column 26, line 26 to column 27, line9, or. A first compartment which contains the composition (A) as definedabove, an optional second compartment contains the composition (A′) asdefined above, when it is present, and a third compartment contains theoxidizing composition (B) as defined above. These devices can beequipped with means which allow the desired mixture to be applied to thehair, such as the devices described in French patent FR-2,586,913, thedisclosure of which is specifically incorporated by reference herein.

[0341] An oxidizing agent, which may be added to the colouringcompositions for carrying out the method according to the inventioncontaining composition, comprises an oxidizing agent and a base.

[0342] Further, this composition comprises for this oxidizing agentcontaining composition customary adjuvant and additives.

[0343] The formulations are for example a solution, especially athickened watery or watery alcoholic solution, a cream, foam, a gel, apowder or an emulsion.

[0344] In general, preference is given to a cream formulation, a gelformulation or a foam formulation, and especially a foam formulation.

[0345] But, if stability- or solubility-problems arise it may ofadvantage to use powder formulation as for example described in DE 19713 698, page 2, line 26 to 54 and page 3, line 51 to page 4, line 25,and page 4, line 41 to page 5 line 59.

[0346] The oxidizing agent (calculated as hydrogen peroxide) is presentin this composition in 0.5 to 12% by weight, in particular from 1 to 6%by weight based on the totals weight of the oxidizing agent containingcomposition.

[0347] The pH-value of the oxidizing agent containing composition isusually about 2 to 7, and in particular about 3 to 6.

[0348] An oxidizing agent free composition, which may be added to thecolouring compositions for carrying out the method according to theinvention, comprises a developer compound and a coupler compound and areduction agent, or

[0349] a developer compound or/and optionally a reduction agent, or

[0350] a coupler compound and a reduction agent.

[0351] Further, an oxidizing agent free composition may additionallycomprise a direct dye as for example described in German PatentApplication 199 59 479, column 3, line 12 to line 16.

[0352] Additionally, the oxidizing agent free composition usuallycomprises customary adjuvant and additives. Preferred are those, whichare described in German Patent Application, in column 3, line 17 to line41.

[0353] The pH-value of the oxidizing agent free composition is usuallyabout 3 to 11, and in particular about 5 to 10, and most particularabout 9 to 10.

[0354] For adjusting the pH-value organic or inorganic acids, as forexample described in German Patent Application 199 59 479, column 3,line 46 to line 53 are suitable.

[0355] The colouring compositions for carrying out the method accordingto the invention may also be combined with hair dye compositionscomprising an acid dye. Hair dye compositions comprising an acid dye areknown. For example, they are described in “Dermatology”, edited by Ch.Culnan, H. Maibach, Verlag Marcel Dekker Inc., New York, Basle, 1986,Vol. 7, Ch. Zviak, The Science of Hair Care, chapter 7, pages 248-250,especially on page 253 and 254.

[0356] The hair dye compositions comprising an acid dye have a pH of2-6, preferably 2-5, more preferably 2.5-4.0. If the pH is too low, theresulting composition may roughen the hair, scalp and hand skin due toan acid component in some cases. If the pH is too high, the penetrationaccelerating effect on the acid dye is lowered.

[0357] The colouring method according to the present invention may alsoreadily be used in combination with other dyes and/or adjuvants used inthe colouring of hair, for example

[0358] acid dye and an alkylene carbonate, as described in U.S. Pat. No.6,248,314, especially in examples 1 and 2, or

[0359] acid hair dye compositions comprise various kinds of organicsolvents represented by benzyl alcohol as a penetrant solvent have goodpenetrability into hair, as described in Japanese Patent ApplicationLaid-Open Nos. 210023/1986 and 101841/1995, or

[0360] acid hair dye compositions with a water-soluble polymer or thelike to prevent the drooping of the hair dye composition, as describedfor example in Japanese Patent Application Laid-Open Nos. 87450/1998,255540/1997 and 245348/1996, or

[0361] acid hair dye compositions with a water-soluble polymer ofaromatic alcohols, lower alkylene carbonates, or the like as describedin Japanese Patent Application Laid-Open No. 53970/1998 and JapanesePatent Invention No. 23911/1973.

[0362] Preferred keratin fibers are human hair.

[0363] The dyes or dye precursors are suitable for all-over colouring ofthe hair, that is to say when colouring the hair on a first occasion,and also for re-colouring subsequently, or colouration of locks or partsof the hair.

[0364] The dyes or dye precursors are applied to hair for examplethrough massage in by hand, a comb, a brush, or a bottle, or a bottle,which is combined with a comb or a nozzle.

[0365] In general, the dyes or dye precursors are applied to the hair ina formulation with further components, like adjuvants or additional dyesor dye precursors.

[0366] After the application of the dyeing composition the dyed hair iscustomary rinsed.

[0367] Customary, the rinsing is conducted with water.

[0368] In a suitable embodiment of the processes of the presentinvention for dyeing human hair, the dyeing composition is not rinsedoff, but washed off with a commercially available hair shampoo.

[0369] In general, the dyed hair is dried after rinsing and/or washing.

[0370] Customary, drying is conducted with hot air by means of a drieror the like, since color migration to clothes and the like becomesscarcely caused.

[0371] In the context of the present invention, the expression “afurther dye”, denotes preferably an oxidation dye, a diazotisedcompound, a capped diazotised compound and/or coupler compound, or aciddye, especially selected a cationic, anionic or uncharged direct dye.

[0372] A very suitable process for dyeing keratin fibers comprisecontacting the keratin fibers under alkaline conditions with at leastone capped diazotized compound and a coupler compound, with the provisothat the pH is adjusted in the range from 2 to 6 in the last processstep. Adjusting the pH is achieved in conventional manner by adding anacid as described for example in EP 962218, especially on page 3, lines12 to 16.

[0373] Acids are for example tartaric acid or citric acid, a citric acidgel, a suitable buffer solution with optionally an acid dye.

[0374] Preferred technical forms of acids are a solution, a gel, acream, a foam, a conditioner, a emulsion, a shampoo and more preferred ashampoo or a conditioner.

[0375] In the context of the present invention, the expression “alkalinecondition”, denotes to all process steps without those wherein acidconditions are explicitly described.

[0376] In general, all processes for dyeing keratin fibers, inparticular human hair, comprise after contacting the keratin fiber witha dye

[0377] a) leaving the fibers to stand, and

[0378] b) then rinsing the fibers.

[0379] The process for dyeing keratin fibers, in particular human hair,with direct dyes comprises

[0380] a) contacting the keratin fibers with a direct dye.

[0381] The process for dyeing is for example described in WO 01/66646 onpage 15, line 32 to page 16, line 2.

[0382] Usually, the dyeing compositions are usually applied to the hairin an amount of from 50 to 100 g.

[0383] This composition is left on the fiber at 15 to 45° C. for 5 to 30minutes, and in particular for 10 to 20 minutes at 20 to 30° C.

[0384] The method of colouring according to the invention in combinationwith at least one direct dye may further concerns a process for dyeingkeratin fibres comprises

[0385] a) contacting the keratin fibers with at least one direct dye, abase and an oxidizing agent.

[0386] Compositions comprising at least one direct dye and an oxidizingagent, are for example described in WO 97/20545, on page 3, line 24 topage 11, line 4, and especially on page 4, line 9 to 17.

[0387] The composition comprising at least one direct dye, a base and anoxidizing agent is prepared by mixing at least one direct dye and abase, and then just before the dyeing of the hair, adding an oxidizingagent.

[0388] Alternatively, the oxidizing agent can be applied simultaneouslywith a composition comprising at least one dye and a base.

[0389] Preferably, the process for dyeing keratin fibres with at leaston direct dye comprises using a multi-compartment dyeing device or‘kits’ as described for example in WO 97/20545, especially on page 4,line 19 to line 27.

[0390] Suitable processes for enlightening dyeing, which can be used incombination with the method for colouring according to the invention aredescribed in WO 97/20545, on page 11 to page 13.

[0391] Suitable processes for dyeing with cationic dyes, which can becornbined with the method of colouring according to the presentinvention, are described

[0392] in WO 95/01772, especially on page 10, line 24 to page 11, line16, and especially on page 11, line 29 to page 28, or

[0393] in WO 01/66646, especially on page 1, line 18 to page 3, line 16,and preferred from page 16, line 20 to page 22, or

[0394] in EP 970 685, especially on page 50, lines 15 to 43, andpreferred from page 50, line 46 to page 51, line 40, or

[0395] in DE-A-19 713 698, especially page 5, lines 26 to 60, or

[0396] a process of dyeing with direct dyes and oxidizing agent isdescribed in WO 97/20545, especially on page 10, line 10 to page 11,line 55 and preferably on page 11, line 6 to page 13, line 19.

[0397] Suitable processes for dyeing with combinations of cationic dyesand other dyes, which can be combined with the method of colouringaccording to the present invention, are:

[0398] mixtures of at least two cationic dyes as described in WO95/01772, especially on page 11, lines 1 to 15, or

[0399] combinations of Pyrazolo-[1,5-a]-pyrimidines with at least onecationic dye as described in EP 998,908, especially on page 50, lines 15to 28, or

[0400] combinations of cationic dyes as described in FR-2788432,especially on page 49, line 28 to page 52, and preferred on page 50,lines 16 to 28, or

[0401] combinations of direct dyes and/or an oxidation dye and oxidizingagents in the form of permanent-wave fixing solution, especially withdirect dyes as described in DE-A-19 713 698, especially on page 2, lines12 to 23, especially on page 4, line 65 to page 5, line 59, or

[0402] combinations of cationic dyes and an oxidation dye of thedeveloper compound type and oxidizing agents as described in EP 850 638,especially on page 29, line 42 to page 30, line 20 and preferred on page30, line 25 to page 32, line 30, or

[0403] combinations of an extemporaneous mixture of a composition (A)containing one or more oxidation dye precursors and optionally one ormore couplers, and of a composition (B), in powder form, containing oneor more direct dye, preferably cationic, optionally dispersed in anorganic pulverulent excipient and/or a mineral pulverulent excipient,and a composition (C) containing one or more oxidizing agent asdescribed in U.S. Pat. No. 6,190,421, especially in column 8, lines 43to 52, and preferably in column 8, line 55 to column 9, line 55, or

[0404] a ready-to-use composition comprising, at least one oxidationbase, at least one cationic direct dye and at least one enzyme of2-electron oxidoreductase type in the presence of at least one donor forthe said enzyme as described in U.S. Pat. No. 6,228,129, especially incolumn 25, line 56 to column 27, line 9, or

[0405] a ready-to-use composition or multi-compartment dyeing devicecomprising compositions of at least one direct cationic dye and at leastone nitrated benzene dye as described in WO 99/20235 on page 34, line 27to page 37, or

[0406] a ready-to-use composition or multi-compartment dyeing devicecomprising compositions of at least one direct cationic dye and at leastone autooxidisable oxidation dye, especially benzene, indol and indolinederivatives as described in WO 99/20234, especially on page 32, line 20to page 35, oxidation dyeing compositions of at least one direct dye andat least one meta-Aminophenol derivative and at least one developercompound and an oxidizing agent as described in EP 850 636, especiallyon page 18, line 1 to page 22, line 11, or

[0407] oxidation dyeing compositions of at least one direct dye and atleast one developer compound selected from the group ofpara-Phenylenediamine derivatives and Bis-Phenylalkylenediamine and, andat least one coupler compound selected from the group of meta-Diphenolsand an oxidizing agent, as described in EP-A-850 637, especially on page19, line 24 to page 22, line 57,

[0408] cationic dye and e.g. a pyrazolo-(1,5-a)-pyrimidine derivatives,as described in EP 998 908, especially on page 47, line 25 to page 50,line 29, or

[0409] arianors and/or oxidative dyes, as described in FR-2 788 432,especially on page 2, line 16 to page 3, line 16, and page 5, line 19 topage 14, line 8, and combinations with cationic dyes as described onpage 14, line 23 and following, or

[0410] oxidative dye precursors (unsaturated aldehyde and couplercompounds), as described in German Patent Application 197 172 24,especially on page 3, line 36 to page 9 line 64.

[0411] The method of colouring of keratin fibers, especially human hair,according to the present invention may combined with direct dyes andoxidative dyes.

[0412] The process for dyeing keratin fibers with direct dyes andoxidative dyes, in particular human hair, comprises

[0413] a) contacting the keratin fibers with an oxidizing agent,optionally containing at least a direct dye,

[0414] b) then contacting the keratin fibers with an oxidizing agentfree composition, optionally containing at least a direct dye,

[0415] or

[0416] a) contacting the keratin fibers with an oxidizing agent freecomposition, optionally containing at least a direct dye,

[0417] b) then contacting the keratin fibers with an oxidizing agent,optionally containing at least a direct dye.

[0418] The method of colouring according to the present invention maycombined with a process for dyeing keratin fibers with direct dyes andoxidative dyes, which comprises

[0419] a) contacting the keratin fibers with at least one direct dye,

[0420] b) then contacting the keratin fibers with an oxidizing agentfree composition.

[0421] Such process is for example described in DE 199 41 450,especially on page 5, lines 50 to 58, and on page 8, line 31 to 46.

[0422] Oxidizing agent is usually applied in form of an oxidizing agentcontaining composition. Oxidizing agent free composition containing atleast one coupler compound, at least one developer compound, a base anda reduction agent.

[0423] Customary, the oxidizing agent containing composition is evenlyapplied in a sufficient amount related to the amount of hair, usuallywith 30 to 200 g.

[0424] In general, the oxidizing agent containing composition is left onthe fiber at 15 to 45° C. for 0 to 15 minutes, and in particular for 0to 5 minutes.

[0425] Then the oxidizing agent free composition is applied to the hair.

[0426] In general, the direct dye and oxidizing agent free compositionis left on the fiber at 15 to 50° C. for 5 to 45 minutes, and inparticular for 10 to 25 minutes.

[0427] The coupler and developer compounds of the oxidizing agent freecomposition can be applied simultaneously or in succession. Preferred isa simultaneous application.

[0428] One preferred embodiment of the process is to wash the hair withshampoo and or a weak acid, such as citric acid or tartrate acid.

[0429] The direct dyes, which are stable to reduction can storedtogether with the oxidizing agent free compositions and are applicableas composition.

[0430] It is of advantage to prepare compositions of direct dyes, whichare not stable to reduction, with oxidizing agent free compositions justbefore the dyeing process.

[0431] Further, a direct dye and an oxidizing agent free composition canbe applied simultaneously or in succession.

[0432] A suitable process for the coloration of keratin fiber withdirect dyes and oxidation dyes, which can be used in combination withthe method of colouring according to the present invention, comprises

[0433] a) mixing at least one direct dye and optionally at least onecoupler compound and at least one developer compound, and an oxidizingagent, which optionally contains at least one direct dye, and

[0434] b) then contacting the keratin fibers with the mixture asprepared in step a).

[0435] A further suitable process for the coloration of keratin fiberwith direct dyes and oxidation dyes, which can be used in combinationwith the method of colouring according to the present invention,comprises

[0436] a) mixing at least one autooxidable compound and at least onedeveloper compound and at least one direct dye, and

[0437] b) then contacting the keratin fibers with the mixture preparedin step a).

[0438] The direct dye is usually applied in form of a composition,comprising further adjuvants, in particular an aqueous composition.

[0439] In general the mixing is conducted just before contacting thekeratin fibers.

[0440] Usually, the mixture prepared in process step a) is evenlyapplied in a sufficient amount related to the amount of hair, usuallywith 30 to 200 g.

[0441] In general, the mixture is left on the fiber at 15 to 45° C. for0 to 50 minutes, and in particular for 30 to 45 minutes.

[0442] One preferred embodiment of the processes is to wash the hairwith shampoo and or a weak acid, such as citric acid or tartrate acid,as for example described in EP 962218, especially on page 3, lines 9 to18.

[0443] In addition, the method of the invention comprises further a twostep, separate application of a direct dye and an oxidation dye. Such anapplication is for example described in DE-A-19 713 698, especially onpage 4, line 65 to page 35, line 59, wherein the keratin fibres arecontacted in a first step with a direct dye, especially in form of atinting powder, and an oxidizing agent, and then, in a second step, withan oxidizing free composition, especially in form of a powder.

[0444] Further, it is possible to apply a for example a ready-to-usecomposition for the oxidation dyeing of keratin fibers, in particularhuman keratin fibers such as hair, as described in U.S. Pat. No.6,190,421, in column 1, line 65 to column 3, line 65, especially incolumn 10, line 62 to column 12, line 65.

[0445] According to this process, the ready-to-use dye composition asdefined above is applied to the fibers and is left on them for anexposure time preferably of from approximately 3 to approximately 40minutes, more preferably from approximately 5 to approximately 30minutes, after which the fibers are rinsed, optionally washed withshampoo, rinsed again and dried.

[0446] If unsaturated aldehydes are used as oxidative precursor dyetogether with a coupler compound no oxidizing agent is needed asdescribed in German Patent Application 19 717 224.5. Nevertheless, itmay be desirable to conduct the colouring in the presence of oxidizingagents, if lightening or a unified colouration of the keratin fiber isenvisaged.

[0447] The process of dyeing keratin fibers with oxidative dyeprecursors, which can be used in combination with the method ofcolouring according to the present invention, comprises

[0448] a) contacting the keratin fibers with an unsaturated aldehyde, acoupler compound and a direct dye.

[0449] In all above-cited dyeing processes it is also possible to applya mixture of coupler compounds /and or developer compounds and/different direct dyes.

[0450] Another preferred embodiment of the processes for oxidativedyeing of keratin fibers, which can be used in combination with themethod of colouring according to the present invention, compriseapplying to the keratin fibers after contacting with an oxidizing agentfree composition containing a coupler compound and a developer compoundand optionally a direct dye with a further oxidizing agent freecomposition containing a coupler compound and a developer compound andoptionally an oxidizing agent containing composition and optionally adirect-dye by a pH range from 5 to 7, preferred from 6.5 to 7. Ingeneral the keratin fiber is not washed or rinsed afterwards as forexample described in EP 962217, especially on page 3, lines 9 to 17.

[0451] The developer and coupler compounds can be applied separately,simultaneously or in succession.

[0452] In all above-cited dyeing processes with oxidation dye precursorsit is also possible to apply a mixture of coupler compounds /and ordeveloper compounds.

[0453] A more suitable process for the dyeing of keratin fibers withoxidative dyes, which can be used in combination with the method ofcolouring according to the present invention, comprises,

[0454] a) contacting the keratin fibers with an oxidizing agentcontaining composition,

[0455] b) then contacting the keratin fibers with an oxidizing agentfree composition.

[0456] Such process is for example described in DE 19959479, especiallyin column 3, line 54 to column 4, line 8.

[0457] Usually, the oxidizing agent containing composition is evenlyapplied in a sufficient amount related to the amount of hair, usuallywith 30 to 200 g.

[0458] In general, the oxidizing agent containing composition is left onthe fiber at 15 to 50° C. for 0 to 15 minutes, and in particular for 0to 30 minutes.

[0459] Then the oxidizing agent free composition is applied.

[0460] Customary, the oxidizing agent free composition is left on thefiber at 15 to 50° C. for 5 to 45 minutes, and in particular for 10 to25 minutes.

[0461] The coupler and developer compounds of oxidizing agent freecompositions can be applied as an admixture, or separatelysimultaneously or in succession. Preferred is the application of anadmixture.

[0462] One suitable embodiment of the processes is to wash the hair withshampoo and or a weak acid, such as citric acid or tartrate acid, as forexample described in EP 962218, especially on page 3, lines 9 to 18.

[0463] A further suitable process for the coloration of keratin fiberwith oxidation dyes, which can be used in combination with the method ofcolouring according to the present invention, comprises

[0464] a) mixing at least one coupler compound and developer compound,and an oxidizing agent, and

[0465] b) then contacting the keratin fibers with the mixture asprepared in step a).

[0466] A further suitable process for the coloration of keratin fiberwith an oxidation dye, which can be used in combination with the methodof colouring according to the present invention, comprises

[0467] a) mixing an autooxidable compound and a developer compound, and

[0468] b) then contacting the keratin fibers with the mixture preparedin step a).

[0469] Especially preferred is a process for dyeing keratin fibers, inparticular human hair, with capped diazotised compounds, whichcomprises,

[0470] a) contacting the keratin fibers, under alkaline conditions, withat least one capped diazotised compound and a coupler compound, andoptionally an oxidising agent, and optionally in the presence of afurther dye,

[0471] b) then adjusting the pH in the range of 6 to 2 by treatment withacid, optionally in the presence of a further dye.

[0472] The capped diazotised compound and coupler compound andoptionally the oxidizing agent, can be applied in any desired ordersuccessively, or simultaneously.

[0473] Preferably, however, the capped diazotised compound and thecoupler compound are applied simultaneously, in a single composition.

[0474] Customary the dyeing composition is applied to the hair in anamount of from 50 to 100 g.

[0475] In the context of the present invention, the expression “alkalineconditions” denotes a pH in the range from 8 to 10, preferably 9-10,especially 9.5-10.

[0476] Adding bases, for example sodium carbonate, ammonia or sodiumhydroxide, to the hair or to the dye precursors, the capped diazotisedcompound and/or the water-soluble coupling component, or to colouringcompositions comprising the dye precursors, customarily achieve thealkaline conditions.

[0477] In the second stage, the diazotised compound and the couplercompound are then caused to react, preferably by lowering the pH to avalue of from 6 to 2, especially from 3 to 4.

[0478] A preferred embodiment of all processes of the present inventionfor dyeing keratin fibers comprise contacting the keratin fibers underalkaline conditions with at least one capped diazotized compound and acoupler compound, with the proviso that the pH is adjusted in the rangefrom 2 to 6 in the last process step.

[0479] Adjusting the pH is achieved in conventional manner by adding anacid as described for example in EP 962218, especially on page 3, lines12 to 16.

[0480] Acids are for example tartaric acid or citric acid, a citric acidgel, a suitable buffer solution with optionally an acid dye.

[0481] Preferred technical forms of acids are a solution, a gel, acream, a foam, a conditioner, a emulsion, a shampoo and more preferred ashampoo or a conditioner.

[0482] The ratio of the amount of alkaline colouring composition appliedin the first stage to that of acid colouring composition applied in thesecond stage is preferably about from 1:3 to 3:1, especially about 1:1.

[0483] This first alkaline and then acid dyeing compositions each areleft on the fiber at 15 to 45° C. for 0.5 to 60 minutes, and inparticular for 5 to 45 minutes at 20 to 30° C.

[0484] In the methods according to the invention, whether or notcolouring is to be carried out in the presence of a further dye willdepend upon the colour shade to be obtained.

[0485] In the context of the present invention, the expression “afurther dye”, denotes preferably an oxidation dye, a diazotisedcompound, a capped diazotised compound and/or coupler compound, or aciddye, especially selected a cabonic, anionic or uncharged direct dye,especially a cationic dye selected from the group of the cationic dyesas described in WO 95/01772, especially on page 2, line 7 to page 4,line 1, and preferred on page 4, line 35 to page 8, line 21 with thegiven preferences, and as described in WO 01/66646, especially on page1, line 18 to page 3, line 16, or a mixture of at least two cationicdyes as described in WO 95/01772, especially on page 8, line 34 to page10, line 22.

[0486] A preferred embodiment of the process for dyeing keratin fibreswith capped diazotised compounds and a coupler compound, comprisescontacting the keratin fibres with more than one capped diazotisedcompound and/or more than one coupler compound.

[0487] Preferred is a process of the present invention for thecoloration of keratin fiber with capped diazotised compounds comprises

[0488] a) mixing, under alkaline conditions, at least one with cappeddiazotised compound and at least one coupler compound and at least onedirect dye and optionally at least one developer compound; and anoxidizing agent, which optionally contains at least one direct dye, and

[0489] b) then contacting the keratin fibers with the mixture asprepared in step a),

[0490] c) then adjusting the pH in the range of 6 to 2 by treatment withacid, optionally in the presence of a further dye.

[0491] More preferred is a process for dyeing keratin fibres with atleast one capped diazotized compound, which comprises

[0492] a) mixing under alkaline conditions, at least one cappeddiazotized compound and at least one direct dye, a base and an oxidizingagent, and

[0493] b) then contacting the keratin fibers with the mixture asprepared in step a),

[0494] c) then adjusting the pH in the range of 6 to 2 by treatment withacid, optionally in the presence of a further dye.

[0495] Further, preferred is a process for the coloration of keratinfiber with capped diazotised compounds comprising

[0496] a) mixing under alkaline conditions, at least one with cappeddiazotised compound and at least one coupler compound and optionally atleast one direct dye and optionally at least one developer compound, andoptionally at least one autooxidable compound, and

[0497] b) then contacting the keratin fibers with the mixture preparedin step a),

[0498] c) then adjusting the pH in the range of 6 to 2 by treatment withacid, optionally in the presence of a further dye.

[0499] A further suitable process for the two-step direct dyeing ofkeratin fibres, which can be used in combination with the method ofcolouring according to the present invention, is characterized in that,

[0500] a) contacting the keratin fibers with an oxidizing agent or anoxidizing agent containing composition,

[0501] b) then contacting the keratin fibers with at least one cappeddiazotised compound and at least a coupler compound and optionally adirect dye or/and optionally an oxidizing agent free composition,

[0502] c) then adjusting the pH in the range of 6 to 2 by treatment withacid, optionally in the presence of a further dye.

[0503] or

[0504] a) contacting the keratin fibers with at least one cappeddiazotised compound and a coupler compound and optionally a direct dyeor/and optionally an oxidizing agent free composition,

[0505] b) then contacting the keratin fibers with an oxidizing agent oran oxidizing agent containing composition,

[0506] c) then adjusting the pH in the range of 5 to 2 by treatment withacid, optionally in the presence of a further dye.

[0507] The present invention also concerns a process for the colourationof keratin fibers, especially human hair, with acid dyes, which can beused in combination with the method of colouring according to thepresent invention.

[0508] The process comprises additionally

[0509] a) contacting the keratin fiber with an acid dye.

[0510] Customary, the dyeing composition comprising an acid dye isapplied to the hair in an amount of from 50 to 100 g.

[0511] This in a composition is left on the fiber at 15 to 45° C. for 1to 30 minutes, and in particular for 0 to 15 minutes at 20 to 30° C.

[0512] Preferably the hair is rinsed and than washed with shampoo andmore preferably not rinsed, but washed with shampoo.

[0513] The shampoo used herein includes a shampoo comprising 5-20% of ausual anionic surfactant such as an alkylsulfate or polyoxyethylenealkylsulfate.

[0514] The colouring compositions used in accordance with the inventionand the optionally used oxidation dye precursors may be stored eitherseparately or together, either in a liquid to paste-like preparation(aqueous or non-aqueous) or in the form of a dry powder. When thecomponents are stored together in a liquid preparation, the preparationshould be substantially anhydrous in order to reduce reaction of thecomponents. When they are stored separately, the reactive components areintimately mixed with one another only immediately before use. In thecase of dry storage, before use a defined amount of hot (from 50 to 80°C.) water is usually added and a homogeneous mixture prepared.

[0515] The following Examples serve to illustrate the method withoutlimiting the method thereto.

[0516] Unless specified otherwise, parts and percentages relate toweight. The amounts of dye specified are relative to the material beingcoloured.

[0517] Special preference is given to colouring compositions for thecolouring of hair. Further additives that are suitable for suchcompositions include additives that are customary in hair-colouring, forexample further dyes, surfactants, solvents, perfumes, polymericadjuvants, thickeners and light stabilisers.

[0518] The diversity of shades and the colour fastness of the colouringcompositions used in accordance with the invention can be increased bycombination with other dyes used in the field of hair-colouringcompositions. They can be combined very readily both with oxidation dyesand with direct dyes, it being possible for the latter to be of anionicnature or uncharged. Only in the case of cationic direct dyes is acertain amount of caution appropriate because in that case precipitationmay, under certain circumstances, occur in the formulation.

[0519] In all colouring compositions, it is also possible for aplurality of different colourants to be used together; likewise, it ispossible for a plurality of different oxidation dye precursors from thegroup of the developer and coupler compounds to be used together, forexample aromatic compounds having a primary or secondary amino group,nitrogen-containing heterocycles, aromatic hydroxy compounds or aminoacids, as described, for example, in German Patent Application 197 17224.5.

[0520] The colouring compositions according to the invention producecolour shades in the range from yellow to blue, and the fastnessproperties are outstanding. Attention is drawn to the excellent fastnessto light and fastness to washing properties and to their property thatenables hair that has already been coloured a dark colour still to bedistinctly altered in shade.

[0521] In a further embodiment, for the purpose of further modificationof colour shades the colouring compositions according to the inventionalso comprise, in addition to the dyes according to the invention,customary direct dyes, for example from the group of the nitroanilines,nitrophenylenediamines, nitroaminophenols, anthraquinones, indophenols,phenazines, phenothiazines and methines.

[0522] Also very suitable for combination with the colouringcompositions according to the invention are cationised nitroaniline andanthraquinone dyes, for example those described in the following patentspecifications: U.S. Pat. No. 5,298,029, U.S. Pat. No. 5,360,930, U.S.Pat. No. 5,169,403, U.S. Pat. No. 5,256,823, U.S. Pat. No. 5,135,543,EP-A-818 193, U.S. Pat. No. 5,486,629 and EP-A-758 547.

[0523] Also, cationic azo dyes, for example according to GB-A-2 319 776,as well as the oxazine dyes described in DE-A-299 12 327 and mixturesthereof with the other direct dyes mentioned therein, are likewisesuitable for combination.

[0524] In addition, the colouring compositions according to theinvention may also comprise naturally occurring dyes, for example hennared, henna neutral, henna black, camomile blossom, sandalwood, blacktea, Rhamnus frangula bark, sage, campeche wood, madder root, catechu,sedre and alkanet root. Such colouring methods are described, forexample, in EP-A-404 868.

[0525] In respect of further customary dye components, reference is madeexpressly to the series “Dermatology”, edited by Ch. Culnan, H. Maibach,Verlag Marcel Dekker Inc., New York, Basle, 1986, Vol. 7, Ch. Zviak, TheScience of Hair Care, chapter 7, pages 248-250 (direct dyes), andchapter 8, pages 264-267 (oxidation dyes), and to “Europäisches Inventarder Kosmetikrohstoffe”, 1996, published by The European Commission,obtainable in diskette form from the Bundesverband der deutschenIndustrie-und Handelsunternehmen fur Arzneimittel, Reformwaren undKörperpflegemittel e.V., Mannheim.

[0526] It is not necessary for the oxidation dye precursors, wherepresent, or for the dyes each to be single compounds, but rather thecolouring compositions according to the invention may additionallycomprise, depending on the preparation procedures for the individualdyes, lesser amounts of further components, provided such components donot have an adverse effect on the colouring result or do not need to beexcluded for other reasons, for example toxicological reasons.

[0527] The colouring compositions according to the invention may alsoreadily be used in combination with other dyes and/or adjuvants used inthe colouring of hair, for example with

[0528] oxidising agents to achieve lightened colorations, as describedin EP-A-810 851,

[0529] oxidising agents in the form of permanent-wave fixing solution,as described in DE-A-197 13 698 or WO 99/40895,

[0530] oxidation dyeing compositions, as described in EP-A-850 636,EP-A-850 637, EP-A-850 638 and EP-A-852 135,

[0531] oxidation dyes in the presence of oxidoreductase enzyme, asdescribed in WO 99/17730 and WO 99/36034,

[0532] autooxidisable oxidation dyes, as described in WO 99/20234, or

[0533] nitrobenzene derivatives, as described in WO 99/20235.

[0534] The colouring compositions according to the invention produceintense colorations even at physiologically tolerable temperatures ofless than 45° C. They are accordingly suitable especially for colouringhuman hair. For use on human hair, the colouring compositions canusually be incorporated into an aqueous cosmetic carrier. Suitableaqueous cosmetic carriers include, for example, creams, emulsions, gelsand also surfactant-containing foaming solutions, e.g. shampoos or otherpreparations, that are suitable for use on keratin-containing fibres.Such forms of use are described in detail in Research Disclosure 42448(August 1999). If necessary, it is also possible to incorporate thecolouring compositions into anhydrous carriers, as described, forexample, in U.S. Pat. No. 3,369,970. The colouring compositionsaccording to the invention are also outstandingly suitable for thecolouring method described in DE-A-3 829 870 using a colouring comb orcolouring brush.

[0535] The colouring compositions according to the invention mayfurthermore comprise any active ingredient, additive or adjuvant knownfor such preparations. The colouring compositions in many cases compriseat least one surfactant, there being suitable in principle anionic andalso zwitterionic, ampholytic and non-ionic surfactants. In many cases,however, it has proved advantageous to select the surfactants fromanionic and non-ionic surfactants.

[0536] Anionic surfactants suitable for use in preparations according tothe invention include any anionic surface-active substance that issuitable for use on the human body. Such a substance is characterised byan anionic group that imparts water solubility, for example acarboxylate, sulfate, sulfonate or phosphate group, and a lipophilicalkyl group having approximately from 10 to 22 carbon atoms. Inaddition, glycol or polyglycol ether groups, ester, ether and amidegroups and also hydroxy groups may be present in the molecule. Examplesof suitable anionic surfactants, each in the form of sodium, potassiumor ammonium salts or mono-, di- or tri-alkanolammonium salts having 2 or3 carbon atoms in the alkanol group, are:

[0537] linear fatty acids having from 10 to 22 carbon atoms (soaps),

[0538] ether carboxylic acids of formula R—O—(CH₂—CH₂—O)_(x)—CH₂—COOH,in which R is a linear alkyl group having from 10 to 22 carbon atoms andx=0 or from 1 to 16,

[0539] acyl sarcosides having from 10 to 18 carbon atoms in the acylgroup,

[0540] acyl taurides having from 10 to 18 carbon atoms in the acylgroup,

[0541] acyl isothionates having from 10 to 18 carbon atoms in the acylgroup,

[0542] sulfosuccinic acid mono- and di-alkyl esters having from 8 to 18carbon atoms in the alkyl group and sulfosuccinic acidmonoalkylpolyoxyethyl esters having from 8 to 18 carbon atoms in thealkyl group and from 1 to 6 oxyethyl groups,

[0543] linear alkanesulfonates having from 12 to 18 carbon atoms,

[0544] linear α-olefin sulfonates having from 12 to 18 carbon atoms,

[0545] α-sulfo fatty acid methyl esters of fatty acids having from 12 to18 carbon atoms,

[0546] alkyl sulfates and alkyl polyglycol ether sulfates of formulaR′—O(CH₂—CH₂—O)_(x)—SO₃H, in which R′ is a preferably linear alkyl grouphaving from 10 to 18 carbon atoms and x′=0 or from 1 to 12,

[0547] mixtures of surface-active hydroxysulfonates according to DE-A-3725 030,

[0548] sulfated hydroxyalkylpolyethylene and/or hydroxyalkylenepropyleneglycol ethers according to DE-A-3 723 354,

[0549] sulfonates of unsaturated fatty acids having from 12 to 24 carbonatoms and from 1 to 6 double bonds according to DE-A-3 926 344,

[0550] esters of tartaric acid and citric acid with alcohols that areaddition products of approximately from 2 to 15 molecules of ethyleneoxide and/or propylene oxide with fatty alcohols having from 8 to 22carbon atoms.

[0551] Preferred anionic surfactants are alkyl sulfates, alkylpolyglycol ether sulfates and ether carboxylic acids having from 10 to18 carbon atoms in the alkyl group and up to 12 glycol ether groups inthe molecule, and also especially salts of saturated and especiallyunsaturated C₈-C₂₂carboxylic acids, such as oleic acid, stearic acid,isostearic acid and palmitic acid.

[0552] The term “zwitterionic surfactants” denotes surface-activecompounds that carry at least one quaternary ammonium group and at leastone —COO⁽⁻⁾ or —SO₃ ⁽⁻⁾ group in the molecule.

[0553] Zwitterionic surfactants that are especially suitable are theso-called betaines, such as the N-alkyl-N,N-dimethylammonium glycinates,for example cocoalkyldimethylammonium glycinate,N-acylaminopropyl-N,N-dimethylammonium glycinates, for examplecocoacylaminopropyldimethylammonium glycinate, and2-alkyl-3-carboxymethyl-3-hydroxyethylimidazolines each having from 8 to18 carbon atoms in the alkyl or acyl group and alsococoacylaminoethylhydroxyethylcarboxymethyl glycinate. A preferredzwitterionic surfactant is the fatty acid amide derivative known by theCTFA name cocamidopropyl betaine.

[0554] Ampholytic surfactants are to be understood as meaningsurface-active compounds that, in addition to a C₈-C₁₈-alkyl or -acylgroup, contain at least one free amino group and at least one —COOH or—SO₃H group in the molecule and are capable of forming internal salts.Examples of suitable ampholytic surfactants include N-alkylglycines,N-alkylpropionic acids, N-alkylaminobutyric acids,N-alkyliminodipropionic acids,N-hydroxyethyl-N-alkylamido-propylglycines, N-alkyltaurines,N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoaceticacids, each having approximately from 8 to 18 carbon atoms in the alkylgroup. Ampholytic surfactants to which special preference is given areN-cocoalkylamino-propionate, cocoacylaminoethylaminopropionate andC₁₂-C₁₈acylsarcosine.

[0555] Non-ionic surfactants contain as the hydrophilic group, forexample, a polyol group, a polyalkylene glycol ether group or acombination of polyol and polyglycol ether groups.

[0556] Such compounds are, for example:

[0557] addition products of from 2 to 30 mol of ethylene oxide and/orfrom 0 to 5 mol of propylene oxide with linear fatty alcohols havingfrom 8 to 22 carbon atoms, with fatty acids having from 12 to 22 carbonatoms and with alkylphenols having from 8 to 15 carbon atoms in thealkyl group,

[0558] C₁₂-C₂₂ fatty acid mono- and di-esters of addition products offrom 1 to 30 mol of ethylene oxide with glycerol,

[0559] C₈-C₂₂alkyl-mono- and -oligo-glycosides and ethoxylated analoguesthereof,

[0560] addition products of from 5 to 60 mol of ethylene oxide withcastor oil and hydrogenated castor oil,

[0561] addition products of ethylene oxide with sorbitan fatty acidesters,

[0562] addition products of ethylene oxide with fatty acidalkanolamides.

[0563] The alkyl-group-containing compounds used as surfactants may besingle substances, but the use as starting materials of natural rawmaterials of vegetable or animal origin is generally preferred in thepreparation of such substances, with the result that the substancemixtures obtained have different alkyl chain lengths according to theparticular starting material used.

[0564] The surfactants that are addition products of ethylene and/orpropylene oxide with fatty alcohols or derivatives of such additionproducts may either be products having a “normal” homologue distributionor products having a restricted homologue distribution. “Normal”homologue distribution is to be understood as meaning mixtures ofhomologues obtained in the reaction of fatty alcohol and alkylene oxideusing alkali metals, alkali metal hydroxides or alkali metal alcoholatesas catalysts. Restricted homologue distributions, on the other hand, areobtained when, for example, hydrotalcites, alkali metal salts of ethercarboxylic acids, or alkali metal oxides, hydroxides or alcoholates areused as catalysts. The use of products having restricted homologuedistribution may be preferred.

[0565] Examples of further active ingredients, adjuvants and additivesare:

[0566] non-ionic polymers, for example vinylpyrrolidone/vinyl acrylatecopolymers, polyvinyl-pyrrolidone and vinylpyrrolidone/vinyl acetatecopolymers and polysiloxanes,

[0567] zwitterionic and amphoteric polymers, for exampleacrylamidopropyl-trimethyl-ammonium chloride/acrylate copolymers andoctylacrylamide/methyl methacrylate/tert-butylaminoethylmethacrylate/2-hydroxypropyl methacrylate copolymers,

[0568] anionic polymers, for example polyacrylic acids, crosslinkedpolyacrylic acids, vinyl acetate/crotonic acid copolymers,vinylpyrrolidone/vinyl acrylate copolymers, vinyl acetate/butylmaleate/isobornyl acrylate copolymers, methyl vinyl ether/maleicanhydride copolymers and acrylic acid/ethylacrylate/N-tert-butylacrylamide terpolymers,

[0569] thickeners, such as agar, guar gum, alginates, xanthan gum, gumarabic, karaya gum, locust bean flour, linseed gums, dextrans, cellulosederivatives, e.g. methyl cellulose, hydroxyalkyl cellulose andcarboxymethyl cellulose, starch fractions and derivatives, such asamylose, amylopectin and dextrins, clays, e.g. bentonite, or fullysynthetic hydrocolloids such as, for example, polyvinyl alcohol,

[0570] structuring agents, such as glucose and maleic acid,

[0571] hair-conditioning compounds, such as phospholipids, for examplesoya lecithin, egg lecithin and cephalins, silicone oils, and alsoconditioning compounds, for example such as those described in DE-A-19729 080, EP-A-834 303 or EP-A-312 343,

[0572] protein hydrolysates, especially elastin, collagen, keratin, milkprotein, soya protein and wheat protein hydrolysates, condensationproducts thereof with fatty acids and also quaternised proteinhydrolysates,

[0573] perfume oils, dimethyl isosorbitol and cyclodextrins,

[0574] solubilisers, such as ethanol, isopropanol, ethylene glycol,propylene glycol, glycerol and diethylene glycol,

[0575] anti-dandruff active ingredients, such as piroctone, olamines andZinc Omadine,

[0576] further substances for adjusting the pH,

[0577] active ingredients such as panthenol, pantothenic acid,allantoin, pyrrolidonecarboxylic acids and salts thereof, plant extractsand vitamins,

[0578] cholesterol,

[0579] light stabilisers and UV absorbers, as described, for example, inEP-A-819 422,

[0580] consistency regulators, such as sugar esters, polyol esters orpolyol alkyl ethers,

[0581] fats and waxes, such as spermaceti, beeswax, montan wax,paraffins, fatty alcohols and fatty acid esters,

[0582] fatty acid alkanolamides,

[0583] polyethylene glycols and polypropylene glycols having a molecularweight of from 150 to 50 000, for example such as those described inEP-A-801 942,

[0584] complexing agents, such as EDTA, NTA and phosphonic acids,

[0585] swelling and penetration substances, such as polyols and polyolethers, as listed extensively, for example, in EP-A-962 219, for exampleglycerol, propylene glycol, propylene glycol monoethyl ether, butylglycol, benzyl alcohol, carbonates, hydrogen carbonates, guanidines,ureas and also primary, secondary and tertiary phosphates, imidazoles,tannins, pyrrole,

[0586] opacifiers, such as latex,

[0587] pearlising agents, such as ethylene glycol mono- and di-stearate,

[0588] propellants, such as propane-butane mixtures, N₂O, dimethylether, CO₂ and air, and also

[0589] antioxidants, for example isoascorbic acid, ascorbic acid, sodiumsulfite, thioglycolic acid and thiolactic acid.

[0590] The constituents of the aqueous carrier are used in thepreparation of the colouring compositions according to the invention inthe amounts customary for that purpose; for example emulsifiers are usedin concentrations of from 0.5 to 30% by weight and thickeners inconcentrations of from 0.1 to 25% by weight of the total colouringcomposition.

[0591] To colour keratin-containing fibres, especially to colour humanhair, the colouring compositions are usually applied to the hair in anamount of from 50 to 100 g in the form of the aqueous cosmetic carrier,left on the hair for approximately 30 minutes and then rinsed off orwashed off with a commercially available hair shampoo.

[0592] The colouring compositions used in accordance with the inventionand the optionally used oxidation dye precursors may be applied to thekeratin-containing fibres either simultaneously or successively, theorder in which they are applied being unimportant.

[0593] The colouring compositions used in accordance with the inventionand the optionally used oxidation dye precursors may be stored eitherseparately or together, either in a liquid to paste-like preparation(aqueous or non-aqueous) or in the form of a dry powder. When thecomponents are stored together in a liquid preparation, the preparationshould be substantially anhydrous in order to reduce reaction of thecomponents. When they are stored separately, the reactive components areintimately mixed with one another only immediately before use. In thecase of dry storage, before use a defined amount of hot water (from 50to 80° C.) is usually added and a homogeneous mixture prepared.

[0594] The following Examples serve to illustrate the invention withoutlimiting the invention thereto. Unless specified otherwise, parts andpercentages relate to weight. The amounts of dye specified are relativeto the material being coloured.

EXAMPLE 1

[0595] A strand of bleached human hair is immersed, for 10 minutes atroom temperature, in an aqueous solution, which has been adjusted to apH of 3 and which contains 1% by weight of the compound of formula

[0596] The impregnated human hair is then washed with water and, at roomtemperature, quickly immersed in an aqueous solution of sodium carbonatehaving a pH of 8.

[0597] The hair is then thoroughly rinsed using water and, whereappropriate, a shampoo solution and is dried. Red-coloured hair isobtained, with outstanding fastness properties, especially fastness towashing properties.

Examples 2 to 5

[0598] Analogously to the colouring method described in Example 1, thecolorations indicated in Table 1 are obtained. TABLE 1 Example Compoundof formula Amount Hair colour 2

1% by weight copper 3

1% by weight orange 4

1% by weight red 5

1% by weight dark-blue

1. A method of colouring keratin-containing fibres, wherein a compoundof formula

wherein R is hydroxy or NHR₁, R₁ being hydrogen or C₁-C₄alkyl, and B isan aromatic or heterocyclic ring, is diazotised, and then fixed on thematerial being coloured.
 2. A method according to claim 1, wherein thereis used, as the compound of formula (1), a compound of formula

wherein R₂ is hydroxy or NHR₁, R₁ being hydrogen or C₁-C₄alkyl, R₃ isC₁-C₄alkyl or sulfo, R₄ is hydroxy or sulfo, R₅ is hydrogen, C₁-C₄alkyl,—COOH or COOC₁-C₄alkyl, R₆ and R₇ are, each independently of the other,hydrogen or C₁-C₄alkoxy, n is a number 0, 1 or 2, and m is a number 0, 1or
 2. 3. A method according to claim 1, wherein the resulting diazoniumsalt is applied at a pH of from 2 to 5 to the material being coloured.4. A method according to claim 1, wherein the diazonium salt is fixed ata pH of from 7.5 to
 10. 5. A method according to claim 1, comprisingapplying a diazonium salt and a further dye.
 6. A colouring composition,for carrying out the method of colouring keratin-containing fibres,according to claim 1, comprising a) at least a compound of formula

wherein R is hydroxy or NHR₁, R₁ being hydrogen or C₁-C₄alkyl, B is anaromatic or heterocyclic ring and A⁻ is an anion, b) a medium foradjusting the pH, c) water and, optionally, d) further additives and/orfurther dyes.
 7. A colouring composition according to claim 6, whichcomprises, as component a), a compound of formula

wherein A₁ ⁻ is a chloride, sulfate, hydrogen sulfate, zinc chloride,fluoroborate, oxalate or 1,5-naphthalenedisulfonate anion or anotheraromatic sulfonate anion.
 8. A method according to claim 1, wherein thekeratin-containing fibres are human hair.